CN108463460A - Kill microorganism oxadiazole derivatives - Google Patents

Kill microorganism oxadiazole derivatives Download PDF

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CN108463460A
CN108463460A CN201780005898.3A CN201780005898A CN108463460A CN 108463460 A CN108463460 A CN 108463460A CN 201780005898 A CN201780005898 A CN 201780005898A CN 108463460 A CN108463460 A CN 108463460A
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alkyl
carbonyl
amino
group
base
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CN108463460B (en
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T·J·霍夫曼
D·斯狄尔利
A·杰恩格纳特
R·比奥德格尼斯
M·波理尔特
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Syngenta Participations AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D473/00—Heterocyclic compounds containing purine ring systems
    • C07D473/02—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6
    • C07D473/04—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms
    • C07D473/06—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms with radicals containing only hydrogen and carbon atoms, attached in position 1 or 3
    • C07D473/08—Heterocyclic compounds containing purine ring systems with oxygen, sulphur, or nitrogen atoms directly attached in positions 2 and 6 two oxygen atoms with radicals containing only hydrogen and carbon atoms, attached in position 1 or 3 with methyl radicals in positions 1 and 3, e.g. theophylline

Abstract

Compound with formula (I)

Description

Kill microorganism oxadiazole derivatives
The present invention relates to killing microorganism oxadiazole derivatives, such as active constituent, Zhe Xie oxadiazole derivatives tool Kill microbial activity, especially Fungicidally active.The invention further relates to include at least one of Zhe Xie oxadiazole derivatives Agrochemical composition, and be related to Zhe Xie oxadiazole derivatives or composition in agricultural or gardening for controlling or prevent The purposes that plant, the cereal crops of harvest, seed or non-living material are infected by phytopathogenic microorganisms, preferred fungi.
WO 2015/185485 describes purposes of the substituted oxadiazoles for fighting plant pathogenic fungi.
According to the present invention, a kind of compound with formula (I) is provided：
Wherein
N is 1 or 2；
A1Indicate N or CR1, wherein R1Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethoxy Base or difluoro-methoxy；
A2Indicate N or CR2, wherein R2Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethoxy Base or difluoro-methoxy；
A3Indicate N or CR3, wherein R3Indicate hydrogen or halogen；
A4Indicate N or CR4, wherein R4Indicate hydrogen or halogen；And
Wherein A1、A2、A3And A4In 0 or 1 or 2 be N；
R5And R6Independently selected from hydrogen, C1-4Alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or
R5And R6Cyclopropyl is formed with together with the carbon atom that they are shared；
Z is selected from Z1、Z2、Z3、Z4、Z5Or Z6；Wherein
Z1It indicates to be keyed to C (R by C-C5)(R6) heterocycle, the wherein heterocyclyl moieties are contained in loop system There is 1 nitrogen and optionally include 5 yuan or 6 yuan of non-aromatic rings of 1,2 or 3 other ring members independently selected from the following group, The group is made of the following terms：O、S、N、NR7, C (O) or S (O)2, condition, which is the heterocycle, cannot contain 2 companies selected from O and S Continuous atom；
Z2It indicates to be keyed to C (R by C-C5)(R6) heteroaryl, the wherein heteroaryl moieties are contained in loop system There is 1 nitrogen-atoms and optionally includes 5 yuan or 6 yuan of aromatics of 1,2 or 3 other ring members independently selected from the following group Ring, the group are made of the following terms：O, S, N or NR7；
R7It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl ammonia Base carbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, C1-4Alkyl sulphonyl, N-C1-2Alkyl amino sulfonyl or N, bis- C of N-1-2Alkane Base amino-sulfonyl；And
Wherein for Z1And Z2, the heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 38Can it is identical or Different substituent group substitutions；
R8Indicate cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, bis- C of N-1-4Alkyl amino Carbonyl or C1-4Alkoxycarbonyl amino；
Z3It indicates to be keyed to C (R by C-N5)(R6) heterocycle, the wherein heterocyclyl moieties are contained in loop system There is 1 nitrogen and optionally include 5 yuan or 6 yuan of non-aromatic rings of 1,2 or 3 other ring members independently selected from the following group, The group is made of the following terms：O、S、N、NR9Or C (=N-O-C1-4Alkyl), condition, which is the heterocycle, cannot contain selected from O and S 2 continuous atoms；
Z4It indicates to be keyed to C (R by C-N5)(R6) heteroaryl, the wherein heteroaryl moieties are contained in loop system There are 5 yuan of aromatic rings of 1 to 4 nitrogen-atoms；
R9It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl ammonia Base carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl；And
Wherein for Z3And Z4, the heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 310Can it is identical or Different substituent group substitutions；
Wherein R10It indicates：
(i) cyano, halogen, hydroxyl, amino, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Haloalkene Base, C1-4Alkoxy, C1-4Alkoxy C1-4Alkyl, C1-4Alkyl alkylthio base, C1-4Halogenated alkoxy, C1-4Alkyl alkylthio base, C1-4Alkane Base sulfinyl, C1-4Alkyl sulphonyl, C1-4Halogenated alkyl sulfanyl, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, Bis- C of N, N-1-4Alkyl amino, formoxyl, hydroxycarbonyl group, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, Amino carbonyl, N-C1-4Alkyl amino-carbonyl, N-C2-4Alkenyl amino carbonyl, N-C2-4Alkynylaminocarbonyl, N, bis- C of N-1-4Alkyl Amino carbonyl, N- morpholines and amino carbonyl, N-C1-4Alkoxy amino carbonyl, N-C1-4Alkyl-N-C1-4Alkoxy amino carbonyl, C1-4Alkoxycarbonyl amino, C1-4Alkoxycarbonyl amino C1-4Alkyl, N-C1-4Alkoxy C1-4Alkyl amino-carbonyl, phenyl carbonyl Oxygroup C1-4Alkyl, benzylcarbonylamino C1-4Alkyl, C1-4Alkyl carbonyl oxy, C1-4Halogenated alkyl carbonyloxy group, C1-4Alkyl carbonyl oxy C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4Alkyl, (C1-4Alkyl)3Si-；Or
(ii)-C(O)N(Ra)(Rb), wherein：
RaIt is hydrogen, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C1-2Halogenated alkoxy C1-4Alkyl, C3-5Alkenyl, C3-5Alkynyl, amino C1-4Alkyl, N-C1-4Alkyl amino C1-4Alkyl, N, N- bis- C1-4Alkyl amino C1-4Alkyl, formoxyl, C1-4Alkyl-carbonyl, C3-4Naphthene base carbonyl, C1-4Halogenated alkyl carbonyl, C1-4Alkyl oxycarbonyl Base C1-4Alkyl, C1-4Alkoxy carbonyl C1-4Alkyl, C1-4Alkyl carbonyl oxy C1-4Alkyl, N-C1-4Alkyl amino-carbonyl C1-4Alkyl, Bis- C of N, N-1-4Alkyl amino-carbonyl C1-4Alkyl, C1-4Alkyl alkylthio base C1-4Alkyl, C1-4Alkyl sulphonyl, C1-4Alkyl sulphonyl C1-4Alkyl, C1-4Alkyl sulfonyl-amino C1-4Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4 Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl or C1-4Haloalkylcarbonylamino C1-4Alkyl, and
RbIt is hydrogen, hydroxyl, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4 Alkyl, C3-4Alkenyl, C3-4Alkynyl, C3-4Naphthenic base, C3-4Naphthenic base C1-2Alkyl, C1-4Alkoxy, C3-4Alkenyloxy group, C3-4Haloalkene Oxygroup, C3-4Alkynyloxy group；Or
RaAnd RbThe nitrogen-atoms being bonded with them, which forms optionally to contain together, is selected from O, S, S (O)2, C (O) and NRc Other hetero atom or group 4 yuan, 5 yuan or 6 membered rings, wherein RcIt is hydrogen, methyl, methoxyl group, formoxyl or acyl group；Or
(iii)-C(O)O-Rd, wherein：
RdIt is hydrogen, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C1-2Alkoxy C1-2Alkoxy C1-4Alkyl, C1-2Halogenated alkoxy C1-4Alkyl, C3-5Alkenyl, C3-4Halogenated alkenyl, C3-4Alkenyloxy group C1-4Alkyl, C3-5Alkynyl, C3-4Alkynyloxy group C1-4Alkyl, N-C1-3Alkyl amino C1-4Alkyl, N, bis--C of N-1-3Alkyl amino C1-4Alkane Base, C1-4Alkoxycarbonyl amino C1-4Alkyl or C1-4Alkyl-carbonyl-amino C1-4Alkyl；Or
Wherein for Z4, the heteroaryl moieties are optionally by 1 selected from R11Substituent group substitution, and optionally further It is selected from R by 1 or 210Can be identical or different substituent group substitution；
Wherein R11It indicates：
(i)C3-8Naphthenic base, C3-8Naphthenic base C1-2Alkyl, N-C3-8Cycloalkyl amino carbonyl, N-C3-8Naphthenic base C1-2Alkyl Amino carbonyl, phenyl, phenyl C1-2Alkyl, phenoxy group C1-2Alkyl, phenyl C1-2Alkyl alkylthio base, heteroaryl moieties therein are Include heteroaryl, the heteroaryl C of 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being individually selected from N, O and S1-2Alkyl, Heteroaryloxy C1-2Alkyl, N- heteroarylaminocarbonyls, Heterocyclylcarbonyl, heterocyclyl moieties therein are independent comprising 1 or 2 Ground is selected from heteroatomic 4 yuan heterocycle, the heterocycle C to 6 yuan of non-aromatic rings of N, O and S1-6Alkyl, benzodioxole Base (benzodioxolyl), and the wherein described naphthenic base, phenyl, heteroaryl, heterocycle and benzodioxole base portion Point any of optionally by 1,2 or 3 be selected from R12Can be identical or different substituent group substitution；Or
(ii)-C(O)N(Re)(Rf), wherein：
ReIt is C3-5Naphthenic base, C3-5Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, heterocyclyl moieties therein are packets Containing 1,2 or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition be The heterocycle cannot contain heterocycle, the heterocycle C of 2 continuous atoms selected from O and S1-2Alkyl, heteroaryl moieties therein are Include heteroaryl, the heteroaryl C of 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being independently chosen from N, O and S1-2Alkyl,
And wherein the naphthenic base, phenyl, heterocycle or heteroaryl moieties optionally by 1 or 2 selected from following item can Replaced with identical or different substituent group：Hydroxyl, amino, formoxyl, acyl group, cyano, halogen, methyl, difluoromethyl, fluoroform Base, methoxyl group, ethyoxyl or difluoro-methoxy or the naphthenic base or heterocyclyl moieties are optionally oxo (=O) by 1 or 2 Group substitution, and
RfIt is hydrogen, C1-4Alkyl, C1-4Alkoxy C1-4Halogenated alkyl, C3-4Alkenyl, C3-4Alkynyl, C3-4Naphthenic base, C3-4Cycloalkanes Base C1-2Alkyl；Or
(iii)-C(O)O-Rg, wherein：
RgIt is C3-5Naphthenic base, C3-5Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, heterocyclyl moieties therein are packets Containing 1,2 or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition be The heterocycle cannot contain heterocycle, the heterocycle C of 2 continuous atoms selected from O and S1-2Alkyl, heteroaryl moieties therein are Include heteroaryl, the heteroaryl C of 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being independently chosen from N, O and S1-2Alkyl,
And wherein the naphthenic base, phenyl, heterocycle or heteroaryl moieties optionally by 1 or 2 selected from following item can Replaced with identical or different substituent group：Hydroxyl, formoxyl, acyl group, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, first Oxygroup, ethyoxyl or difluoro-methoxy or the naphthenic base or heterocyclyl moieties are optionally by 1 or 2 base for oxo (=O) Group's substitution；Or
(iv)(C1-4Alkyl)-O-N=C (Rh)-、(C1-4Halogenated alkyl)-O-N=C (Rh)-、(C2-4Alkenyl)-O-N=C (Rh)、(C2-4Alkynyl)-O-N=C (Rh)-, benzyl-O-N=C (Rh)-, wherein RhIt is hydrogen or methyl；
R12It is cyano, fluorine, chlorine, bromine, methyl, ethyl, formoxyl, methoxyl group, ethyoxyl, difluoromethyl, trifluoromethyl, two Fluorine methoxyl group or ethoxy carbonyl；
Z5It indicates to be keyed to C (R by C-N5)(R6) miscellaneous two ring group, wherein the miscellaneous two ring group part is in loop system In containing 1 nitrogen and optionally include 7 yuan to 10 yuan of 1,2 or 3 other ring members independently selected from the following group full With fractional saturation or partially aromatic fused ring system, which is made of the following terms：O、S、N、NR13, C (O) or S (O)2, condition 2 continuous atoms selected from O and S cannot be contained by being miscellaneous two ring group；
Z6It indicates to be keyed to C (R by C-N5)(R6) miscellaneous diaryl, wherein the miscellaneous biaryl moiety is in loop system In 9 yuan of two aromatic systems containing 1 to 4 nitrogen-atoms；
R13It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl ammonia Base carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl；And
Wherein for Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally selected from R by 1,2,3 or 414Can be with Identical or different substituent group substitution；
R14It is cyano, halogen, hydroxyl, formoxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, cyano C1-4 Alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, Bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, Bis- C of N, N-1-4Alkyl amino-carbonyl or C1-4Alkoxycarbonyl amino, and in addition for Z5, it is oxo (=O)；Or
Wherein for Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally selected from R by 115Substituent group substitution, And optionally further R is selected from by 1 or 214Can be identical or different substituent group substitution；
R15It is pyridyl group, benzodioxole base oxygroup, phenoxy group or Phenylsulfanyl, wherein phenoxy group and phenyl Sulfanyl is optionally by can be identical or different 1,2 or 3 selected from chlorine, fluorine, bromine, methyl, ethyl, methoxyl group and ethyoxyl A substituent group substitution；Or
Its salt or N- oxides.
Unexpectedly, it is actual purpose, it has been found that the compounds with formula (I) have highly beneficial level Bioactivity, for protecting the plants from the infringement of fungus-caused disease.
According to the second aspect of the invention, the agricultural of the compound with formula (I) comprising effective fungicidal amount is provided Chemical composition that.
According to the third aspect of the invention we, it provides control or prevents useful plant from being infected by phytopathogenic microorganisms Method, wherein using compound of the effective fungicidal amount with formula (I) or comprising this compound as the combination of active constituent Object is applied to the plant, its part or its place.
According to the fourth aspect of the invention, purposes of the compound with formula (I) as fungicide is provided.According to this This particular aspects of invention, the purposes can not include the method for treating human body or animal body by operation or therapy.
As used herein, term " halogen (halogen or halo) " refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromine, bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine.
As used herein, cyano means-CN groups.
As used herein, amino means-NH2Group.
As used herein, hydroxyl means-OH groups.
As used herein, term " C1-6Alkyl " refers to the hydrocarbon for the linear chain or branched chain being only made of carbon atom and hydrogen atom Chain group, the hydrocarbon chain radical are free of unsaturation, have from one to six carbon atom, and it is attached to this point by singly-bound The remainder of son.Term " C1-4Alkyl " and " C1-2Alkyl " should be interpreted accordingly.“C1-C6Alkylidene ", " C1-4Alkylidene ", Or " C1-2Alkylidene " group refers respectively to C1-6Alkyl, C1-4Alkyl or C1-2The corresponding definition of alkyl, the difference is that described Group is the remainder that molecule is attached to by two singly-bounds.C1-6The example of alkyl includes but not limited to methyl, ethyl, different Propyl, n-propyl and tertiary butyl.
As used herein, term " C1-4Alkoxy " refers to formula-ORaGroup, wherein RaIt is as above general definition C1-4Alkyl group.C1-4The example of alkoxy includes but not limited to methoxyl group, ethyoxyl and propoxyl group.
As used herein, term " C1-4Alkoxy C1-4Alkyl " refers to formula Rb-O-RaGroup, wherein RbBe as On the C that generally defines1-4Alkyl group, and RaIt is the C as above generally defined1-4Alkylidene group.
As used herein, term " C1-4Alkyl alkylthio base " refers to formula-SRaGroup, wherein RaIt is as above general The C of definition1-4Alkyl group.
As used herein, term " C1-4Alkyl sulphinyl " refers to formula-S (O) RaGroup, wherein RaIt is as above The C generally defined1-4Alkyl group.
As used herein, term " C1-4Alkyl sulphonyl " refers to formula-S (O)2RaGroup, wherein RaIt is as above The C generally defined1-4Alkyl group.
As used herein, term " C2-4Alkenyl " refer to the straight chain being only made of carbon atom and hydrogen atom or branch Hydrocarbon chain radical, the hydrocarbon chain radical contain it is at least one can be (E)-configuration or (Z)-configuration double bond, have from two to four Carbon atom is attached to the remainder of molecule by singly-bound.Term " C3-4Alkenyl " should be interpreted accordingly.C2-4The reality of alkenyl Example includes but not limited to vinyl and propyl- 1- alkenyls.
As used herein, term " C2-4Alkynyl " refer to the straight chain being only made of carbon atom and hydrogen atom or branch Hydrocarbon chain radical, the hydrocarbon chain radical include at least one three key, are had from two to four carbon atom, and it is attached to by singly-bound The remainder of molecule.Term " C3-4Alkynyl " should be interpreted accordingly.C2-4The example of alkynyl includes but not limited to acetenyl, propyl- 1- alkynyls, propargyl (Propargyl), butyl- 1- alkynyls.
As used herein, term " C3-4Alkenyloxy group " refers to formula-ORaGroup, wherein RaIt is as above general definition C3-4Alkenyl group.
As used herein, term " C3-4Alkynyloxy group " refers to formula-ORaGroup, wherein RaIt is as above general definition C3-4Alkynyl group.
As used herein, term " C1-4Alkoxy carbonyl " refers to formula-C (O) ORaGroup, wherein RaIt is as above The C generally defined1-C4Alkyl group.
As used herein, term " C1-4Alkyl-carbonyl " refers to formula-C (O) RaGroup, wherein RaIt is as above one As the C that defines1-4Alkyl group.
As used herein, term " formoxyl " refers to the group for having formula-C (O) H.
As used herein, term " hydroxycarbonyl group " refers to the group for having formula-C (O) OH.
As used herein, term " C1-4Alkyl carbonyl oxy " refers to formula-OC (O) RaGroup, wherein RaIt is as above The C generally defined1-4Alkyl group.
As used herein, term " C1-4Halogenated alkoxy " refers to former by one or more same or different halogens The C as defined above of son substitution1-4Alkoxy base.C1-4The example of halogenated alkoxy includes but not limited to fluorine methoxyl group, fluorine second Oxygroup, trifluoromethoxy, trifluoro ethoxy.
As used herein, term " C1-4Halogenated alkyl " refers to by one or more same or different halogen atoms The C as above generally defined of substitution1-4Alkyl group.C1-4The example of halogenated alkyl includes but not limited to methyl fluoride, fluoro ethyl, two Methyl fluoride and trifluoromethyl.
As used herein, term " C1-4Halogenated alkyl sulfanyl " refers to by one or more same or different halogen The C as above generally defined of plain atom substitution1-4Alkyl alkylthio base group.
As used herein, term " C2-4Halogenated alkenyl " refers to by one or more same or different halogen atoms The C as above generally defined of substitution2-4Alkenyl group.
As used herein, term " C3-8Naphthenic base " refers to saturation or part unsaturation and includes 3 to 8 carbon atoms Stabilization monocycle or bicyclic group.C3-6Naphthenic base should be interpreted accordingly.C3-8The example of naphthenic base includes but not limited to：Ring third Base, cyclobutyl, cyclopenta and cyclohexyl.
As used herein, term " C3-8Naphthenic base C1-2Alkyl " refers to by C as defined above1-2Alkylidene group is attached It is connected to the C as defined above of the remainder of molecule3-8Cycloalkyl ring.Term " C3-6Naphthenic base C1-2Alkyl " and " C3-4Naphthenic base C1-2Alkyl " should be interpreted accordingly.C3-8Naphthenic base C1-2The example of alkyl includes but not limited to Cyclopropyl-methyl, cyclobutyl-second Base and cyclopenta-propyl.
As used herein, term " C3-8Cycloalkyl amino carbonyloxy group " refers to formula-C (O) NRaGroup, wherein Ra It is the C as above generally defined3-8Group of naphthene base.
As used herein, term " N-C3-8Naphthenic base C1-2Alkyl amino-carbonyl " refers to formula-C (O) NRaBase Group, wherein RaIt is C as defined above3-8Naphthenic base C1-2Alkylidene group.
As used herein, term " C1-4Alkoxycarbonyl amino " refers to formula-NH-C (O)-O-RaGroup, Middle RaIt is C as defined above1-4Alkyl group.
As used herein, term " C1-4Alkoxycarbonyl amino C1-4Alkyl " refers to formula-RaC(O)NHRbBase Group, wherein RaIt is C as defined above1-4Alkoxy base, and RbIt is C as defined above1-4Alkylidene group.
As used herein, term " C1-4Alkyl carbonyl oxy " refers to formula-OC (O) RaGroup, wherein RaIt is as above The C generally defined1-4Alkyl group.
As used herein, term " C1-4Alkyl carbonyl oxy C1-4Alkyl " refers to formula-RaOC(O)RbGroup, wherein RaIt is the C as above generally defined1-4Alkylidene group, and RbIt is the C as above generally defined1-4Alkyl.
As used herein, oxo means=O groups, such as ketone group (- C (O) -), sulfinyl (- S (O) -) or sulphonyl Base (- S (O)2) oxygen.
As used herein, amino carbonyl means-C (O) NH2Group.
As used herein, term " N-C1-4Alkyl amino " refers to formula-NH-RaGroup, wherein RaIt is as above fixed The C of justice1-4Alkyl group.
As used herein, term " bis- C of N, N-1-4Alkyl amino " refers to formula-N (Ra)-RaGroup, wherein each RaIt is C that as defined above can be identical or different1-4Alkyl group.
As used herein, term " bis- C of N, N-1-4Alkyl amino-carbonyl " refers to formula-C (O) NRa(Pa) group, Wherein each RaIt is the C that can be identical or different as above generally defined1-4Alkyl group.
As used herein, term " N-C1-4Alkyl amino-carbonyl " refers to formula-C (O) NHRaGroup, wherein RaIt is As above the C generally defined1-4Alkyl group.
As used herein, term " N-C2-4Alkenyl amino carbonyl " refers to formula-C (O) NHRaGroup, wherein RaIt is As above the C generally defined2-4Alkenyl group.
As used herein, term " N-C2-4Alkynylaminocarbonyl " refers to formula-C (O) NHRaGroup, wherein RaIt is As above the C generally defined2-4Alkynyl group.
As used herein, term " N-C1-4Alkoxy C1-4Alkyl amino-carbonyl " refers to formula-C (O) NHRaORb's Group, wherein RaIt is the C as above generally defined1-4Alkylidene group, and RbIt is the C as above generally defined1-4Alkyl group.
As used herein, term " N-C1-4Alkoxy amino carbonyl " refers to formula-C (O) NHORaGroup, wherein RaIt is the C as above generally defined1-4Alkyl group.
As used herein, term " N-C1-4Alkyl-N-C1-4Alkoxy amino carbonyl " refers to formula-C (O) N (Ra) ORbGroup, wherein RaIt is the C as above generally defined1-4Alkyl group, and RbIt is the C as above generally defined1-4Alkyl group (with RaIt is identical or different).
As used herein, term " phenyl carbonyloxy group C1-4Alkyl " refers to formula Rb-C(O)ORaGroup, wherein Rb It is phenyl group, and Ra is the C as above generally defined1-4Alkylidene group.
As used herein, term " benzylcarbonylamino C1-4Alkyl " refers to formula Rb-C(O)NHRaGroup, Middle RbIt is phenyl group, and Ra is the C as above generally defined1-4Alkylidene group.
As used herein, term " C1-4Alkyl-carbonyl-amino C1-4Alkyl " refers to formula Rb-C(O)NHRaGroup, Wherein RbIt is C1-4Alkyl group, and RaIt is the C as above generally defined1-4Alkylidene group.
As used herein, term " phenyl C1-2Alkyl " refers to by C as defined above1-2Alkylidene group is attached to point The benzyl ring of the remainder of son.
As used herein, term " phenoxy group C1-2Alkyl " refers to by C as defined above1-2Alkylidene group is attached to The phenoxy group ring of the remainder of molecule.
As used herein, term " phenyl C1-2Alkyl alkylthio base " refers to-SRaGroup, wherein RaIt is benzene as defined above Base C1-2Alkyl group.
As used herein, term " aryl " refers to the aromatic ring systems being only made of carbon atom and hydrogen atom, the virtue Race's loop system can be monocycle, two rings or tricyclic.The example of such loop system includes phenyl, naphthalene, anthryl, indenyl Or phenanthryl.
As used herein, term " heteroaryl " (unless otherwise defined) refer to comprising 1,2,3 or 4 be independently chosen from nitrogen, Heteroatomic 5 yuan or 6 yuan of aromatic monocyclic groups of oxygen and sulphur.The heteroaryl groups can be bonded through carbon atom or hetero atom.It is miscellaneous The example of aryl includes but not limited to furyl, pyrrole radicals, thienyl, pyrazolyl, imidazole radicals, thiazolyl, isothiazolyl, oxazoles Base, isoxazolyls, triazolyl, tetrazole radical, pyrazinyl, pyridazinyl, pyrimidine radicals or pyridyl group.
As used herein, term " heteroaryl C1-2Alkyl " refers to by C as defined above1-2Alkylidene group is attached to The heteroaryl ring of the remainder of molecule.
As used herein, term " heteroaryloxy C1-2Alkyl " refers to formula-RaORbGroup, wherein RaIt is as above The C generally defined1-2Alkylidene group, and RbIt is heteroaryloxy group as defined above.
As used herein, term " miscellaneous diaryl " refers to (unless otherwise defined) being individually selected from comprising 1,2,3 or 4 9 yuan or 10 yuan of bicyclic aromatic ring system systems of the heteroatomic stabilization of nitrogen, oxygen and sulphur.The miscellaneous diaryl group can through carbon atom or Hetero atom is bonded to the remainder of molecule.The example of miscellaneous diaryl includes but not limited to indyl, indazolyl, benzimidazole Base, pyrrolopyridinyl or triazolo pyridyl.
As used herein, term " heterocycle " or " heterocycle " refer to (unless otherwise defined) independent comprising 1,2 or 3 4 yuan, 5 yuan or 6 yuan non-aromatic mono-cyclic radicals of the heteroatomic stabilization selected from nitrogen, oxygen and sulphur.The heterocyclyl groups can be through carbon Atom or hetero atom are bonded to the remainder of molecule.The example of heterocycle includes but not limited to azetidinyl, oxa- ring Butane group, pyrrolinyl, pyrrolidinyl, Thietane base, tetrahydrofuran base, tetrahydro-thienyl, tetrahydro thiapyran base, piperidines Base, piperazinyl, THP trtrahydropyranyl, morpholinyl or perhydroazepinyl Zhuo Ji.
As used herein, term " heterocycle C1-6Alkyl " refers to by C as defined above1-6Alkylidene group is attached to The heterocyclic ring of the remainder of molecule.Term " heterocycle C1-4Alkyl " and " heterocycle C1-2Alkyl " should be interpreted accordingly.
As used herein, term " benzodioxole base " means following group：
The presence of one or more possible asymmetric carbon atoms means these chemical combination in the compound with formula (I) Object can exist with chiral isomeric form, i.e. the form of enantiomter or diastereoisomer.As around the limited of singly-bound Rotation as a result, there is likely to be atropisomers.Formula (I) is intended to include the possible isomeric form of all that and its mixing Object.The present invention includes the possible isomeric form of all that and its mixture for the compound with formula (I).Similarly, When it is present, formula (I) is intended to include all possible tautomer (including lactams-lactim tautomerism and ketone-alkene Alcohol tautomerism).The present invention includes all possible tautomeric form of the compound with formula (I).
In each case, the compound according to the present invention with formula (I) is in free form, in covalently hydration shape Formula is in oxidised form as N- oxides or in salt form (for example, being subjected in available or agrochemicals on agronomy Salt form).
N- oxides are the oxidised form of tertiary amine or the oxidised form of nitrogenous heteroaromatics.For example, A.Albini and Entitled " the Heterocyclic N- that S.Pietra was published in 1991 in Boca Raton (Boca Raton) CRC publishing houses Them are described in oxides [heterocyclic N-oxides] " books.
Following table provides substituent group n, A about the compound with formula (I)1、A2、A3、A4、R1、R2、R3、R4、R5、R6、Z (Z1、Z2、Z3、Z4、Z5、Z6)、R7、R8、R9、R10(including Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh)、R11、R12、R13、R14And R15's Definition, including preferably define.For any one of these substituent groups, any definition given below can be combined with Lower or any definition of any other substituent group given elsewhere in this document.
N is 1 or 2.In one embodiment of the invention, n is 1.In another embodiment of the present invention, n is 2.
When n is 2, Z passes through minimum neighbouring A1To A4C (the R of loop system5)(R6) segment is connected to the remainder of the molecule Point.
In another embodiment of the present invention, a kind of compound with formula (I) is provided, wherein
A1Indicate N or CR1, wherein R1Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethoxy Base or difluoro-methoxy；
A2Indicate N or CR2, wherein R2Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethoxy Base or difluoro-methoxy；
A3Indicate N or CR3, wherein R3Indicate hydrogen or halogen；
A4Indicate N or CR4, wherein R4Indicate hydrogen or halogen；And
Wherein A1To A4In not more than two be N；
R5And R6Independently selected from hydrogen, C1-4Alkyl, halogen, cyano, trifluoromethyl and difluoromethyl；Or R5And R6Together with Carbon atom attached by them forms cyclopropyl together；
Z is selected from Z1、Z2、Z3、Z4、Z5Or Z6；Wherein
Z1It indicates to be keyed to C (R by C-C5)(R6) heterocycle, wherein heterocyclic moiety be in loop system contain 1 nitrogen And optionally include 5 yuan or 6 yuan of non-aromatic rings of 0,1,2 or 3 other ring members independently selected from the following group, the group It is made of the following terms：O、S、N、NR7, C (O) or S (O)2, condition, which is the heterocycle, cannot contain 2 coherent originals selected from O and S Son；
Z2It indicates to be keyed to C (R by C-C5)(R6) heteroaryl, wherein heteroaryl moieties are to contain 1 in loop system A nitrogen-atoms and 5 yuan or 6 yuan of aromatics for optionally including 0,1,2 or 3 other ring members independently selected from the following group Ring, the group are made of the following terms：O, S, N or NR7；
R7It is C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl amino Carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl；
Wherein for Z1And Z2, the heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 38Can it is identical or Different substituent group substitutions；
R8Indicate cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, bis- C of N-1-4Alkyl amino Carbonyl or C1-4Alkoxycarbonyl amino；
Z3It indicates to be keyed to C (R by C-N5)(R6) heterocycle, wherein heterocyclyl moieties be in loop system contain 1 Nitrogen and 5 yuan or 6 yuan of non-aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, the group It is made of the following terms：O, S, N or NR9, condition, which is the heterocycle, cannot contain 2 coherent atoms selected from O and S；
Z4It indicates to be keyed to C (R by C-N5)(R6) heteroaryl, wherein heteroaryl moieties are to contain 1 in loop system To 5 yuan of aromatic rings of 4 nitrogen-atoms；
R9It is C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl amino Carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl；And
Wherein for Z3And Z4, heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 310Can be identical or not Same substituent group substitution；
R10Indicate cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Alkoxy C1-4Alkyl, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, Bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, Bis- C of N, N-1-4Alkyl amino-carbonyl, C1-4Alkoxycarbonyl amino, C1-4Alkoxycarbonyl amino C1-4Alkyl, phenyl carbonyloxy group C1-4Alkyl phenyl carbonylamino C1-4Alkyl, C1-4Alkyl carbonyl oxy, C1-4Alkyl carbonyl oxy C1-4Alkyl, (C1-4Alkyl)3Si-；
Wherein for Z4, any heteroaryl moieties are optionally by 1 selected from R11Substituent group substitution, and further optionally Ground is selected from R by 1 or 210Substituent group substitution；
R11Indicate C3-8Naphthenic base, C3-8Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, phenyl oxygroup C1-2Alkyl, In heteroaryl moieties be the heteroaryl for including 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being individually selected from N, O and S Base, heteroaryl C1-2Alkyl, heteroaryloxy C1-2Alkyl, heterocyclyl moieties therein are to be individually selected from N, O and S comprising 1 or 2 Heteroatomic 4 yuan heterocycle, the heterocycle C to 6 yuan of non-aromatic rings1-6Alkyl, and the wherein described naphthenic base, phenyl, heteroaryl Any of base and heterocyclyl moieties are optionally selected from R by 1,2 or 312Can be identical or different substituent group substitution；
R12Indicate hydrogen, cyano, fluorine, chlorine, bromine, methyl, ethyl, methoxyl group, ethyoxyl, difluoromethyl, trifluoromethyl or two Fluorine methoxyl group；
Z5It indicates to be keyed to C (R by C-N5)(R6) miscellaneous two ring group, wherein miscellaneous two ring group part is in loop system 7 yuan to 10 yuan containing 1 nitrogen and optionally comprising 0,1,2 or 3 other ring members independently selected from the following group are full With fractional saturation or partially aromatic fused ring system, which is made of the following terms：O, S, N or NR13, C (O) or S (O)2, item Part, which is miscellaneous two ring group, cannot contain 2 coherent atoms selected from O and S；
Z6It indicates to be keyed to C (R by C-N5)(R6) miscellaneous diaryl, wherein miscellaneous biaryl moiety is in loop system 9 yuan of two aromatic systems containing 1 to 4 nitrogen-atoms；
R13It is C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl amino Carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl；
Wherein for Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally selected from R by 1,2 or 314Can be identical Or different substituent group substitution；
R14Indicate cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, bis- C of N-1-4Alkyl amino Carbonyl or C1-4Alkoxycarbonyl amino.
In other embodiments of the invention：
A1Indicate N or CR1, wherein R1Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethoxy Base or difluoro-methoxy.Preferably, A1Indicate CR1, wherein R1Be hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, Methoxyl group, ethyoxyl or difluoro-methoxy.It is highly preferred that R1It is hydrogen or halogen, and even more preferably R1It is hydrogen.
A2Indicate N or CR2, wherein R2Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethoxy Base or difluoro-methoxy.Preferably, A2Indicate CR2, wherein R2Be hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, Methoxyl group, ethyoxyl or difluoro-methoxy.It is highly preferred that R2It is hydrogen or halogen, and even more preferably R2It is hydrogen.
A3Indicate N or CR3, wherein R3Indicate hydrogen or halogen.Preferably, A3Indicate CR3, wherein R3It is hydrogen or halogen.It is more excellent Selection of land, R3It is hydrogen or fluorine, and even more preferably R3It is hydrogen.
A4Indicate N or CR4, wherein R4Indicate hydrogen or halogen.Preferably, A4Indicate CR4, wherein R4It is hydrogen or halogen.It is more excellent Selection of land, R4It is hydrogen or fluorine, and even more preferably R4It is hydrogen.
In the compound according to formula (I), A1、A2、A3And A4In be no more than two (i.e. 0,1 or 2) be N.
In some embodiments of the invention, A1It is N or CR1, wherein R1Indicate hydrogen, chlorine, fluorine, methyl, methoxyl group or trifluoro Methyl, and A2、A3And A4It is C-H.Preferably, A1It is N, and A2、A3And A4It is C-H；Or A1It is C-F, and A2、A3And A4 It is C-H；Or A1It is C-C1, and A2、A3And A4It is C-H；Or A1、A2、A3And A4It is C-H.It is highly preferred that A1、A2、A3And A4It is C-H.In other embodiments of the invention, A3It is CR3, and R3It is halogen (such as fluorine or chlorine), and A1、A2And A4It is C- H。
In some embodiments of the invention, including A1To A46- membered rings be phenyl (wherein A1、A2、A3And A4It is C-H), Pyridyl group (wherein A1It is N and A2、A3And A4It is C-H or A3It is N, and A1、A2And A4C-H), fluorophenyl (wherein A1It is C- F and A2、A3And A4It is C-H or A3It is C-F and A1、A2And A4C-H) or difluorophenyl (for example, wherein A1And A2It is C-F And A3And A4It is C-H or A1And A3It is C-F and A2And A4It is C-H) group.
R5And R6Independently selected from hydrogen, C1-4Alkyl, halogen, cyano, trifluoromethyl and difluoromethyl or R5And R6With it Shared carbon atom form cyclopropyl together.R5It is hydrogen, C1-4Alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, and And preferably hydrogen, C1-4Alkyl, halogen or cyano.R6It is hydrogen, C1-4Alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, and And preferably hydrogen, C1-4Alkyl, halogen or cyano.Preferably, R5It is hydrogen, and R6It is C1-4Alkyl, preferably methyl or ethyl.It is more excellent Selection of land, R5And R6It is hydrogen or R5It is hydrogen and R6It is methyl.
Z is selected from Z1、Z2、Z3、Z4、Z5Or Z6。
In some embodiments of the invention, Z is Z1.In other embodiments of the invention, Z is Z2。
In other embodiments of the invention, Z is Z3.In other embodiments of the invention, Z is Z4.In its of the present invention In his embodiment, Z is Z5.In other embodiments of the invention, Z is Z6.Preferably, Z is Z4Or Z6。
Z1It indicates to be keyed to C (R by C-C5)(R6) heterocycle, wherein heterocyclyl moieties are to contain 1 in loop system A nitrogen and 5 yuan or 6 yuan of non-aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, should Group is made of the following terms：O、S、N、NR7, C (O) or S (O)2, condition is that the heterocycle cannot be continuous containing 2 selected from O and S Atom.Z1Can be selected from pyrrolidinyl, piperidyl, imidazolidinyl, pyrazolidinyl, piperazinyl, oxazolidine radical, isoxazole alkyls, 4,5- dihydro-oxazole bases, morpholinyl, thiazolidinyl, thiazolinyl, sulfenyl morpholinyl.
Preferably, Z1Optionally include 1 other ring members, is selected from O, S, N, NR7, C (O) or S (O)2, and more It is preferred that O or S.According to an embodiment of the invention, Z1It is included in the miscellaneous of the 5 yuan or 6 yuan non-aromatic rings in loop system with 1 nitrogen Ring group part.
Z2It indicates to be keyed to C (R by C-C5)(R6) heteroaryl, wherein heteroaryl moieties are to contain 1 in loop system A nitrogen-atoms and 5 yuan or 6 yuan of aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, The group is made of the following terms：O, S, N or NR7。Z2It can be selected from pyrrole radicals, pyrazolyl, imidazole radicals, triazolyl, tetrazole radical, oxazoles Base, isoxazolyls, thiazolyl, isothiazolyl, oxadiazolyls, thiadiazoles, pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, triazine Base.Preferably, Z2Optionally include 1 or 2 and other is selected from O, S, N or NR7Ring members.It is highly preferred that Z2It is pyridyl group, Specifically pyridine -2- bases, pyridin-3-yl or pyridin-4-yl.
According to an embodiment of the invention, Z2It is following heteroaryl moieties, for 5 yuan with 1 nitrogen in loop system Or 6 yuan of aromatic rings.
For Z1And Z2, heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 38Can be identical or different Substituent group replaces.Preferably for Z1And Z2, heterocycle or heteroaryl moieties are optionally selected from R by 1 or 28Can be identical Or different substituent group substitution.More preferably, for Z1And Z2, heterocycle or heteroaryl moieties are optionally by selected from R81 take Replace for base.
R7It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl ammonia Base carbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, C1-4Alkyl sulphonyl, N-C1-2Alkyl amino sulfonyl or N, bis- C of N-1-2Alkane Base amino-sulfonyl.Preferably, R7It is hydrogen or methyl.
R8Indicate cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, bis- C of N-1-4Alkyl amino Carbonyl or C1-4Alkoxycarbonyl amino.Preferably, R8Indicate cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy.It is highly preferred that R8Indicate cyano, chlorine, fluorine, hydroxyl Base, methyl, ethyl, difluoromethyl, trifluoroethyl, methoxyl group, ethyoxyl, trifluoromethoxy.
Z3It indicates to be keyed to C (R by C-N5)(R6) heterocycle, wherein heterocyclyl moieties are to contain 1 in loop system A nitrogen and 5 yuan or 6 yuan of non-aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, should Group is made of the following terms：O、S、N、NR9Or C (=N-O-C1-4Alkyl), condition is that the heterocycle cannot be containing 2 selected from O and S A continuous atom.Preferably, Z3Optionally include 1 and other is selected from O, S, N or NR9Ring members.Z3It can be selected from pyrroles Alkyl, piperidyl, imidazolidinyl, pyrazolidinyl, piperazinyl, oxazolidine radical, isoxazole alkyls, 4,5- dihydro-oxazoles base, morpholine Base, thiazolidinyl, thiazolinyl, sulfenyl morpholinyl.
According to an embodiment of the invention, Z3It is included in the miscellaneous of the 5 yuan or 6 yuan non-aromatic rings in loop system with 1 nitrogen Loop section.
Z4It indicates to be keyed to C (R by C-N5)(R6) heteroaryl, wherein heteroaryl moieties are to contain 1 in loop system To 5 yuan of aromatic rings of 4 nitrogen-atoms.Preferably, Z4It is pyrrole radicals, pyrazolyl, imidazole radicals, triazolyl, tetrazole radical.
Specifically, Z4(according to optionally substitution of the invention) can be selected from：
It is highly preferred that Z4It is pyrazol-1-yl or triazolyl.Work as Z4When being triazolyl, it can be 1,2,3-triazoles -1- bases, 1,2,3-triazoles -2- bases, 1,2,4- triazole-4-yls or 1,2,4- triazol-1-yls, and most preferably 1,2,4- triazol-1-yls or 1,2,3-triazoles -1- bases.
Z4Can be following heteroaryl moieties, for 5 yuan of aromatic rings with single nitrogen in loop system.However, In some embodiments, Z4It can further include 1 or 2 other ring members selected from O, S and N.
For Z3And Z4, heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 310Can be identical or different Substituent group replaces, or for Z4, heteroaryl moieties are optionally by selected from R111 substituent group substitution, and optionally further It is selected from R by 1 or 210Can be identical or different substituent group substitution.
Preferably for Z4, heteroaryl moieties are optionally by selected from R10Can be identical or different 1 substituent group or 2 A substituent group substitution or heteroaryl moieties are optionally by selected from R11The substitution of 1 substituent group, and optionally further by 1 Selected from R10Substituent group substitution.For Z4, heteroaryl moieties are optionally by 1 selected from R10Substituent group substitution or heteroaryl Part is optionally selected from R by 111Substituent group substitution.
R9It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl ammonia Base carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl.Preferably, R9It is hydrogen or methyl.
R10It indicates (i), (ii) or (iii), wherein：
(i) cyano, halogen, hydroxyl, amino, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Haloalkene Base, C1-4Alkoxy, C1-4Alkoxy C1-4Alkyl, C1-4Halogenated alkoxy, C1-4Alkyl alkylthio base, C1-4Alkyl sulphinyl, C1-4 Alkyl sulphonyl, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, formoxyl, hydroxyl carbonyl Base, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, amino carbonyl, N-C1-4Alkyl amino-carbonyl, N-C2-4 Alkenyl amino carbonyl, N-C2-4Alkynylaminocarbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, N- morpholines and amino carbonyl, N-C1-4Alkane Oxygroup amino carbonyl, N-C1-4Alkyl-N-C1-4Alkoxy amino carbonyl, C1-4Alkoxycarbonyl amino, C1-4Alkoxy carbonyl ammonia Base C1-4Alkyl, N-C1-4Alkoxy C1-4Alkyl amino-carbonyl, phenyl carbonyloxy group C1-4Alkyl, benzylcarbonylamino C1-4Alkyl, C1-4Alkyl carbonyl oxy, C1-4Halogenated alkyl carbonyloxy group, C1-4Alkyl carbonyl oxy C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4Alkyl, (C1-4Alkyl)3Si-；Or
(ii)-C(O)N(Ra)(Rb), wherein：
RaIt is hydrogen, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C1-2Halogenated alkoxy C1-4Alkyl, C3-5Alkenyl, C3-5Alkynyl, amino C1-4Alkyl, N-C1-4Alkyl amino C1-4Alkyl, N, N- bis- C1-4Alkyl amino C1-4Alkyl, formoxyl, C1-4Alkyl-carbonyl, C3-4Naphthene base carbonyl, C1-4Halogenated alkyl carbonyl, C1-4Alkyl oxycarbonyl Base C1-4Alkyl, C1-4Alkoxy carbonyl C1-4Alkyl, C1-4Alkyl carbonyl oxy C1-4Alkyl, N-C1-4Alkyl amino-carbonyl C1-4Alkyl, Bis- C of N, N-1-4Alkyl amino-carbonyl C1-4Alkyl, C1-4Alkyl alkylthio base C1-4Alkyl, C1-4Alkyl sulphonyl, C1-4Alkyl sulphonyl C1-4Alkyl, C1-4Alkyl sulfonyl-amino C1-4Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4 Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl, C1-4Haloalkylcarbonylamino C1-4Alkyl, and
RbIt is hydrogen, hydroxyl, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4 Alkyl, C3-4Alkenyl, C3-4Alkynyl, C3-4Naphthenic base, C3-4Naphthenic base C1-2Alkyl, C1-4Alkoxy, C3-4Alkenyloxy group, C3-4Haloalkene Oxygroup, C3-4Alkynyloxy group；Or
RaAnd RbThe nitrogen-atoms being bonded with them, which forms optionally to contain together, is selected from O, S, S (O)2, C (O) and NRc Other hetero atom or group 4 yuan, 5 yuan or 6 membered rings, wherein RcIt is hydrogen, methyl, methoxyl group, formoxyl or acyl group；Or
(iii)-C(O)O-Rd, wherein：
RdIt is hydrogen, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C1-2Alkoxy C1-2Alkoxy C1-4Alkyl, C1-2Halogenated alkoxy C1-4Alkyl, C3-5Alkenyl, C3-4Halogenated alkenyl, C3-4Alkenyloxy group C1-4Alkyl, C3-5Alkynyl, C3-4Alkynyloxy group C1-4Alkyl, N-C1-3Alkyl amino C1-4Alkyl, N, bis--C of N-1-3Alkyl amino C1-4Alkane Base, C1-4Alkoxycarbonyl amino C1-4Alkyl or C1-4Alkyl-carbonyl-amino C1-4Alkyl.
Preferably, R10(specifically, when Z is Z4When) indicate cyano, halogen, hydroxyl, amino, C1-4Alkyl, C1-4Alkyl halide Base, C1-4Alkoxy, C1-4Alkoxy C1-4Alkyl, C1-4Alkyl alkylthio base, C1-4Halogenated alkyl sulfanyl, N, bis- C of N-1-4Alkyl ammonia Base, formoxyl, hydroxycarbonyl group, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, amino carbonyl, N-C1-4Alkyl amino-carbonyl, N-C2-4 Alkynylaminocarbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, N- morpholines and amino carbonyl, N-C1-4Alkoxy amino carbonyl, N-C1-4 Alkyl-N-C1-4Alkoxy amino carbonyl, C1-4Alkoxycarbonyl amino C1-4Alkyl, N-C1-4Alkoxy C1-4Alkyl amino-carbonyl, Benzylcarbonylamino C1-4Alkyl, C1-4Alkyl carbonyl oxy C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4Alkyl, (C1-4Alkyl)3Si-。
It is highly preferred that R10(specifically, when Z is Z4When) indicate cyano, fluorine, chlorine, bromine, iodine, hydroxyl, amino, methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl, tertiary butyl, difluoromethyl, trifluoromethyl, methoxyl group, ethyoxyl, ethyoxyl Methyl, methoxy ethyl, methylsulfanyl, Ethylsulfanyl, n-propyl sulfanyl, difluoromethyl sulfanyl, trifluoromethyl sulphur Alkyl, dimethylamino, formoxyl, hydroxycarbonyl group, methyl carbonyl, methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, Isopropoxy carbonyl, tert-butoxycarbonyl, amino carbonyl, methylaminocarbonyl, ethyl aminocarbonyl, iodopropynylbutylcarbamate carbonyl (including propargyl-amino carbonyl), morpholine and amino carbonyl, N- Methoxyaminos carbonyl, N- methyl-N-methoxies amino carbonyl, N, N- Dimethylaminocarbonyl, N, N- diethylaminocarbonyls, tertbutyloxycarbonylamino methyl, methoxyethylamino carbonyl Base, benzylcarbonylamino (dimethyl) methyl, methyl carbonyl oxy-methyl, mentioned methylcarbonylamino ethyl, trimethyl silyl.
In some currently preferred embodiments of the present invention, R10Selected from hydroxycarbonyl group, methoxycarbonyl, ethoxy carbonyl, positive third Epoxide carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, amino carbonyl, methylaminocarbonyl, ethyl aminocarbonyl, propargyl Amino carbonyl, N- morpholines and amino carbonyl, N, N- Dimethylaminocarbonyls, N, N- diethylaminocarbonyls, N- methyl-N- methoxies Base amino carbonyl or N- Methoxyamino carbonyls.In some other preferred embodiments, R10Selected from hydroxycarbonyl group, methoxyl group carbonyl Base, ethoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methylaminocarbonyl and ethyl aminocarbonyl.
In other embodiments of the invention, R10It is cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4 Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Alkyl, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N- C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4 Alkyl amino-carbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, C1-4Alkoxycarbonyl amino, C1-4Alkoxycarbonyl amino C1-4Alkane Base, phenyl carbonyloxy group C1-4Alkyl phenyl carbonylamino C1-4Alkyl, C1-4Alkyl carbonyl oxy, C1-4Alkyl carbonyl oxy C1-4Alkyl or (C1-4Alkyl)3Si-。
R11It indicates (i), (ii), (iii) or (iv), wherein：
(i)C3-8Naphthenic base, C3-8Naphthenic base C1-2Alkyl, N-C3-8Cycloalkyl amino carbonyl, N-C3-8Naphthenic base C1-2Alkyl Amino carbonyl, phenyl, phenyl C1-2Alkyl, phenoxy group C1-2Alkyl, phenyl C1-2Alkyl alkylthio base, heteroaryl moieties therein are Include heteroaryl, the heteroaryl C of 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being individually selected from N, O and S1-2Alkyl, Heteroaryloxy C1-2Alkyl, N- heteroarylaminocarbonyls, Heterocyclylcarbonyl, heterocyclyl moieties therein are independent comprising 1 or 2 Ground is selected from heteroatomic 4 yuan heterocycle, the heterocycle C to 6 yuan of non-aromatic rings of N, O and S1-6Alkyl, benzodioxole Base (benzodioxolyl), and the wherein described naphthenic base, phenyl, heteroaryl, heterocycle and benzodioxole base portion Point any of optionally by 1,2 or 3 be selected from R12Can be identical or different substituent group substitution；Or
(ii)-C(O)N(Re)(Rf), wherein：
ReIt is C3-5Naphthenic base, C3-5Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, heterocyclyl moieties therein are packets Containing 1,2 or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition be The heterocycle cannot contain heterocycle, the heterocycle C of 2 continuous atoms selected from O and S1-2Alkyl, heteroaryl moieties therein are Include heteroaryl, the heteroaryl C of 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being independently chosen from N, O and S1-2Alkyl,
And wherein the naphthenic base, phenyl, heterocycle or heteroaryl moieties optionally by 1 or 2 selected from following item can Replaced with identical or different substituent group：Hydroxyl, amino, formoxyl, acyl group, cyano, halogen, methyl, difluoromethyl, fluoroform Base, methoxyl group, ethyoxyl or difluoro-methoxy or the naphthenic base or heterocyclyl moieties are optionally oxo (=O) by 1 or 2 Group substitution, and
RfIt is hydrogen, C1-4Alkyl, C1-4Alkoxy C1-4Halogenated alkyl, C3-4Alkenyl, C3-4Alkynyl, C3-4Naphthenic base or C3-4Ring Alkyl C1-2Alkyl；Or
(iii)-C(O)O-Rg, wherein：
RgIt is C3-5Naphthenic base, C3-5Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, heterocyclyl moieties therein are packets Containing 1,2 or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition be The heterocycle cannot contain heterocycle, the heterocycle C of 2 continuous atoms selected from O and S1-2Alkyl, heteroaryl moieties therein are Include heteroaryl, the heteroaryl C of 1,2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic ring for being independently chosen from N, O and S1-2Alkyl,
And wherein the naphthenic base, phenyl, heterocycle or heteroaryl moieties optionally by 1 or 2 selected from following item can Replaced with identical or different substituent group：Hydroxyl, formoxyl, acyl group, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, first Oxygroup, ethyoxyl or difluoro-methoxy or the naphthenic base or heterocyclyl moieties are optionally by 1 or 2 base for oxo (=O) Group's substitution；Or
(iv)(C1-4Alkyl)-O-N=C (Rh)-、(C1-4Halogenated alkyl)-O-N=C (Rh)-、(C2-4Alkenyl)-O-N=C (Rh)、(C2-4Alkynyl)-O-N=C (Rh)-, benzyl-O-N=C (Rh)-, wherein RhIt is hydrogen or methyl；
Preferably, R11(specifically, when Z is Z4When) indicate cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, phenyl, ring third Base amino carbonyl, Cyclopropyl-methyl-amino carbonyl, phenoxymethyl, Benzylsulfanyl, pyrazolyl, imidazole radicals, thienyl, pyridine Base, pyridyloxymethyl, benzodioxole base.
Preferably, R11It is C3-8Naphthenic base, C3-8Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, phenyl oxygroup C1-2Alkane Base, heteroaryl, heteroaryl C1-2Alkyl, heteroaryloxy C1-2Alkyl, heterocycle or heterocycle C1-6Alkyl.
R12Indicate cyano, fluorine, chlorine, bromine, methyl, ethyl, formoxyl, methoxyl group, ethyoxyl, difluoromethyl, trifluoromethyl, Difluoro-methoxy or ethoxy carbonyl.Preferably, R12It is cyano, fluorine, chlorine, bromine, methyl, ethyl, methoxyl group, ethyoxyl, difluoro Methyl, trifluoromethyl or difluoro-methoxy.
Z5It indicates to be keyed to C (R by C-N5)(R6) miscellaneous two ring group, wherein miscellaneous two ring group part is in loop system 7 yuan to the 10 yuan saturations containing 1 nitrogen and optionally comprising 1,2 or 3 ring members independently selected from the following group in addition, Fractional saturation or partially aromatic fused ring system, the group are made of the following terms：O、S、N、NR13, C (O) or S (O)2, condition is Miscellaneous two ring group cannot contain 2 continuous atoms selected from O and S.Z5It can be selected from penta pyrrole radicals of ring, tetrahydrochysene purine radicals.
Z6It indicates to be keyed to C (R by C-N5)(R6) miscellaneous diaryl, wherein miscellaneous biaryl moiety is in loop system 9 yuan of two aromatic systems containing 1 to 4 nitrogen-atoms；Preferably, Z6Indicate miscellaneous containing 1,2 or 3 nitrogen-atoms in loop system Diaryl.Z6It can be selected from indyl, benzimidazolyl, benzotriazole base (including benzotriazole -1- bases and benzotriazole -2- Base), indazolyl, pyrrolopyridinyl.
For Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally selected from R by 1,2,3 or 414Can it is identical or Different substituent group substitutions, or for Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally by selected from R151 substituent group Substitution, and optionally further R is selected from by 1 or 214Can be identical or different substituent group substitution.For Z6, miscellaneous two virtue Base portion point is optionally selected from R by 1 or 214Substituent group substitution that can be identical or different, or for Z6, miscellaneous diaryl portion Divide optionally by selected from R151 substituent group substitution, and optionally further by 1 be selected from R14Substituent group substitution.
R13It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl ammonia Base carbonyl or N, bis- C of N-1-4Alkyl amino-carbonyl.Preferably, R13It is hydrogen or methyl.
R14Indicate cyano, halogen, hydroxyl, formoxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, cyano C1-4Alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl ammonia Base, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino Carbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl or C1-4Alkoxycarbonyl amino, and in addition for Z5, it is oxo (=O).It is preferred that Ground, R14Indicate fluorine, chlorine, bromine, methyl, ethyl, formoxyl, difluoromethyl, trifluoromethyl, cyano methyl, methoxyl group, ethyoxyl, Methyl carbonyl, methoxycarbonyl, ethoxy carbonyl.
Preferably, R14It is cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4It is halogenated Alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl Amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, bis- C of N-1-4Alkane Base amino carbonyl or C1-4Alkoxycarbonyl amino.
R15It is pyridyl group, benzodioxole base oxygroup, phenoxy group or Phenylsulfanyl, wherein phenoxy group and phenyl Sulfanyl is optionally by can be identical or different 1,2 or 3 selected from chlorine, fluorine, bromine, methyl, ethyl, methoxyl group and ethyoxyl A substituent group substitution.
Preferably, the compound 1.1 to 1.312 listed in table T1 (hereafter) is selected from according to the compound of formula (I).
Preferably, in the compound according to formula (I) of the present invention：
N is 1；
A1It is N or CR1, wherein R1Indicate hydrogen, chlorine, fluorine, methyl, methoxyl group or trifluoromethyl；
A2、A3And A4It is C-H；
R5And R6It is hydrogen or R5It is hydrogen and R6It is methyl；
Z is Z4, selected from pyrrole radicals, pyrazolyl, imidazole radicals, triazolyl, tetrazole radical, and optionally selected by 1,2 or 3 From R10Substituent group substitution that can be identical or different, or optionally by selected from R11The substitution of 1 substituent group, and optionally Further R is selected from by 1 or 210Substituent group substitution；
R10Indicate cyano, fluorine, chlorine, bromine, iodine, hydroxyl, amino, methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, tertiary butyl, difluoromethyl, trifluoromethyl, methoxyl group, ethyoxyl, ethoxyl methyl, methoxy ethyl, methylsulfanyl, second Base sulfanyl, n-propyl sulfanyl, difluoromethyl sulfanyl, Trifluoromethylsulfanyl, formoxyl, hydroxycarbonyl group, methyl carbonyl, Methoxycarbonyl, ethoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methylaminocarbonyl, ethyl aminocarbonyl, third Alkynylaminocarbonyl, Dimethylaminocarbonyl, tertbutyloxycarbonylamino methyl, methoxyethylamino carbonyl, phenylcarbonyl group Amino (dimethyl) methyl, methyl carbonyl oxy-methyl, mentioned methylcarbonylamino ethyl, trimethyl silyl；
R11It is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, phenyl, cyclopropylaminocarbonyl, Cyclopropyl-methyl-amino carbonyl Base, phenoxymethyl, Benzylsulfanyl, imidazole radicals, thienyl, pyridyl group, pyridyloxymethyl, benzodioxole Base, wherein any of the naphthenic base, phenyl, heteroaryl and benzodioxole base part are optionally by 1,2 Or 3 be selected from R12Can be identical or different substituent group substitution；And
R12Be cyano, fluorine, chlorine, bromine, methyl, ethyl, formoxyl, methoxyl group, ethyoxyl, difluoromethyl, trifluoromethyl or Difluoro-methoxy.
It is highly preferred that
N is 1；
A1It is N, and A2、A3And A4It is C-H；Or A1It is C-F, and A2、A3And A4It is C-H；Or A1It is C-Cl, and A2、A3And A4It is C-H；Or A1、A2、A3And A4It is C-H；
R5And R6It is hydrogen；
Z is Z4, it is selected from Z4, it is pyrazol-1-yl or triazolyl, and be optionally selected from R by 1 or 210Can be identical Or different substituent group substitutions, or optionally by selected from R11The substitution of 1 substituent group, and be optionally further selected from by 1 R10Substituent group substitution；
R10Indicate cyano, fluorine, chlorine, bromine, iodine, hydroxyl, amino, methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, tertiary butyl, difluoromethyl, trifluoromethyl, methoxyl group, ethyoxyl, ethoxyl methyl, methoxy ethyl, methylsulfanyl, second Base sulfanyl, n-propyl sulfonyl, difluoromethyl sulfanyl, Trifluoromethylsulfanyl, formoxyl, hydroxycarbonyl group, methyl carbonyl, Methoxycarbonyl, ethoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, methylaminocarbonyl, ethyl aminocarbonyl, third Alkynylaminocarbonyl, Dimethylaminocarbonyl, tertbutyloxycarbonylamino methyl, methoxyethylamino carbonyl, phenylcarbonyl group Amino (dimethyl) methyl, methyl carbonyl oxy-methyl, mentioned methylcarbonylamino ethyl, trimethyl silyl；
R11It is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, phenyl, cyclopropylaminocarbonyl, Cyclopropyl-methyl-amino carbonyl Base, phenoxymethyl, Benzylsulfanyl, imidazole radicals, thienyl, pyridyl group, pyridyloxymethyl, benzodioxole Base, wherein any of the naphthenic base, phenyl, heteroaryl and benzodioxole base part are optionally by 1,2 Or 3 be selected from R12Can be identical or different substituent group substitution；And
R12Be cyano, fluorine, chlorine, bromine, methyl, ethyl, formoxyl, methoxyl group, ethyoxyl, difluoromethyl, trifluoromethyl or Difluoro-methoxy.
Even further preferably,
N is 1；
A1、A2、A3And A4It is C-H；
R5And R6It is hydrogen；
Z is Z4, selected from pyrazol-1-yl, 1,2,3-triazoles -1- bases or 1,2,4- triazol-1-yls, wherein pyrazol-1-yl Optionally R is selected from by 110Or R11Substituent group substitution, wherein R10It is hydroxycarbonyl group, methoxycarbonyl, ethoxy carbonyl, different Propoxycarbonyl, tert-butoxycarbonyl, methylaminocarbonyl or ethyl aminocarbonyl, and R11It is cyclopropylaminocarbonyl, ring Butylamino carbonyl, cyclopentylaminocarbonyl or cyclohexylaminocarbonyl, and 1,2,3-triazoles -1- bases or 1,2,4- triazoles - 1- bases are optionally selected from R by 110Or R11Substituent group substitution, wherein R10It is cyano, acetenyl, fluorine, chlorine, methyl, ethyl, three Methyl fluoride, methoxyl group, ethoxy carbonyl or ethoxyl methyl, and R11It is cyclopropyl.
Preferably, in the compound according to formula (I) of the present invention：
N is 1；
A1It is N or CR1, wherein R1Indicate hydrogen, chlorine, fluorine, methyl, methoxyl group or trifluoromethyl；
A2、A3And A4It is C-H；
R5And R6It is hydrogen or R5It is hydrogen and R6It is methyl；
Z is Z6, it is selected from indyl, indazolyl, benzimidazolyl, pyrrolopyridinyl or triazolo pyridyl, and Optionally R is selected from by 1,2 or 314Substituent group substitution that can be identical or different, or optionally by selected from R151 substitution Base replaces, and is optionally further selected from R by 1 or 214Substituent group substitution；
R14Indicate fluorine, chlorine, bromine, methyl, ethyl, formoxyl, difluoromethyl, trifluoromethyl, cyano methyl, methoxyl group, second Oxygroup, methyl carbonyl, methoxycarbonyl, ethoxy carbonyl；And
R15It is pyridyl group, benzodioxole base oxygroup, phenoxy group or Phenylsulfanyl, wherein phenoxy group and phenyl Sulfanyl is optionally by can be identical or different 1,2 or 3 selected from chlorine, fluorine, bromine, methyl, ethyl, methoxyl group and ethyoxyl A substituent group substitution.
It is highly preferred that
N is 1；
A1、A2、A3And A4It is C-H；
R5And R6It is hydrogen；
Z is Z6, it is selected from indyl, indazolyl, benzimidazolyl, pyrrolopyridinyl or triazolo pyridyl, and Optionally R is selected from by 1 or 214Substituent group substitution that can be identical or different, or optionally by selected from R151 substituent group Substitution, and optionally further R is selected from by 114Substituent group substitution；
R14Indicate fluorine, chlorine, bromine, methyl, ethyl, formoxyl, difluoromethyl, trifluoromethyl, cyano methyl, methoxyl group, second Oxygroup, methyl carbonyl, methoxycarbonyl, ethoxy carbonyl；And
R15It is pyridyl group, benzodioxole base oxygroup, phenoxy group or Phenylsulfanyl, wherein phenoxy group and phenyl Sulfanyl is optionally by can be identical or different 1,2 or 3 selected from chlorine, fluorine, bromine, methyl, ethyl, methoxyl group and ethyoxyl A substituent group substitution.
The compound of the present invention can be the chemical combination with formula (I) (as n=1) such as indicated by formula (Ia) or formula (Ib) The enantiomter of object, wherein R5And R6It is different substituents.
Similarly, when being bonded to R5And R6On one of two carbon locations place R5And R6It is different substituents and another R at one carbon location5And R6When identical, the compound of the present invention can be enantiomter (as n=2).Alternatively, when It is bonded to R5And R6On two carbon locations in each at R5And R6When different, the compound with formula (I) can be with right and wrong pair Reflect isomers (as n=2).
It should be understood that when in an aqueous medium, the compound according to the present invention with formula (I) can with it is corresponding CF3The form (that is, compound with formula (I-I) and formula (I-II) as shown below) being covalently hydrated at oxadiazole motif It is reversible evenly to exist.This dynamic equilibrium may be important the bioactivity of the compound with formula (I).About this hair N, A of the bright compound with formula (I)1、A2、A3、A4、R1、R2、R3、R4、R5、R6、Z(Z1、Z2、Z3、Z4、Z5、Z6)、R7、R8、 R9、R10(including Ra、Rb、Rc、Rd)、R11(including Re、Rf、Rg、Rh)、R12、R13、R14And R15Title is commonly available to formula (I-I) and the compound of formula (I-II), together with n, A shown in table 1.1 to 1.12 (hereafter)1、A2、A3、A4、R1、R2、R3、 R4、R5、R6、Z(Z1、Z2、Z3、Z4、Z5、Z6)、R7、R8、R9、R10(including Ra、Rb、Rc、Rd)、R11(including Re、Rf、Rg、Rh)、R12、 R13、R14And R15Or the specific of combination for the compound 1.1 to 1.312 according to the present invention listed in table T1 (hereafter) drapes over one's shoulders Dew.
The compound of the present invention can be prepared, wherein (unless otherwise stated) is every as shown in following scheme 1 to 10 The definition of one variable is as above in relation to defined in the compound with formula (I).
Compound with formula (I) can be made from the compound (wherein X is halogen, preferably Cl, Br or I) with formula (II) It is standby, by 25 DEG C with 110 DEG C at a temperature of between at suitable solvent (such as dimethylformamide or tetrahydrofuran) In in alkali (such as K2CO3、Cs2CO3Or NaH) in the presence of handled with the compound of formula (III).In some cases Under, better reactivity can be obtained by using catalyst (for example, NaI or 4-dimethylaminopyridine) and microwave radiation Energy.For related example, referring to：WO 2013/132253 and Garcia, M. et al. Org.Biomol.Chem. are [organic and raw Object molecular chemistry] (2004), 11,1633.This reaction is shown in scheme 1.
Scheme 1
In addition, the compound with formula (I) (wherein preferably n is 1) can from the compound with formula (IV) prepare and Come, by 25 DEG C with 75 DEG C at a temperature of between in suitable solvent (such as tetrahydrofuran or ethyl alcohol) in alkali (for example, pyridine Or 4-dimethylaminopyridine) in the presence of handled with trifluoroacetic anhydride.About related example, referring to 2003/028729 Hes of WO WO 2010/045251.This reaction is shown in scheme 2.
Scheme 2
Compound with formula (IV) can be prepared from the compound with formula (V), by 0 DEG C with 100 DEG C it Between at a temperature of handled with hydroxylamine hydrochloride in the presence of alkali (such as triethylamine) in suitable solvent (such as methanol).About phase Example is closed, referring to Kitamura, S. et al. Chem.Pharm.Bull. [chemistry is notified to pharmacy] (2001), 49,268 and WO 2013/066838.This reaction is shown in scheme 3.
Scheme 3
Compound with formula (V) can be prepared from the compound (wherein Y is Br or I) with formula (VI), be passed through In suitable solvent (for example, dimethylformamide or N- crassitudes at raised temperature between 100 DEG C and 120 DEG C Ketone) in suitable cyanide reagent (such as Pd (0)/Zn (CN)2Or CuCN) carry out metal promoted reaction.About related real Example, referring to US 2007/0155739 and WO 2009/022746.This reaction is shown in scheme 4.
Scheme 4
Compound with formula (VI) (wherein preferably n is 1) can (wherein X be halogen from the compound with formula (VII) Element, preferably Cl, Br or I) be prepared, by a temperature of between 25 DEG C with 110 DEG C in suitable solvent (such as dimethyl Formamide or tetrahydrofuran) in alkali (such as K2CO3、Cs2CO3Or NaH) in the presence of with formula (III) compound into Row processing.It in some cases, can be with by using catalyst (for example, NaI or 4-dimethylaminopyridine) and microwave radiation Obtain better reactivity worth.For related example, referring to：WO 2013/132253 and Garcia, M. et al. Org.Biomol.Chem. [organic and biological molecular chemistry] (2004), 11,1633.This reaction is shown in scheme 5.
Scheme 5
Compound (wherein n is that 1 and X is Cl or Br) with formula (II) can be from the compound system with formula (VIII) It is standby, by the presence of ultraviolet light at a temperature of between 55 DEG C with 100 DEG C in suitable solvent (such as four chloromethanes Alkane) middle halogen source (such as N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS)) and radical initiator (such as (PhCO2)2Or azodiisobutyronitrile (AIBN)) handled.About related example, referring to Liu, S. et al. Synthesis [synthesis] (2001), 14,2078 and Kompella, A. et al. Org.Proc.Res.Dev. [organic working research With exploitation] (2012), 16,1794.This reaction is shown in scheme 6.
Scheme 6
Alternatively, the compound with formula (II) can be prepared from the compound with formula (IX), by 25 DEG C with 75 DEG C at a temperature of between in suitable solvent (such as tetrahydrofuran or ethyl alcohol) in alkali (for example, pyridine or 4- dimethyl Aminopyridine) in the presence of handled with trifluoroacetic anhydride.About related example, referring to WO 2003/028729 and WO 2010/ 045251.This reaction is shown in scheme 7.
Scheme 7
Compound with formula (IX) can be prepared from the compound with formula (X), by 0 DEG C with 100 DEG C it Between at a temperature of handled with hydroxylamine hydrochloride in the presence of alkali (such as triethylamine) in suitable solvent (such as methanol).About phase Example is closed, referring to Kitamura, S. et al. Chem.Pharm.Bull. [chemistry is notified to pharmacy] (2001), 49,268 and WO 2013/066838.This reaction is shown in scheme 8.
Scheme 8
Compound (wherein Y is Br, I or CN and X is C1, Br or I) with formula (VII) is commercially available, or can be with Be prepared from the compound with formula (XI), by 55 DEG C with 100 DEG C at a temperature of between in suitable solvent (such as tetrachloro Methane) in the presence of uv light use halogen source (for example, N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS)) and radical initiator is (such as (PhCO2)2Or azodiisobutyronitrile (AIBN)) handled.About related example, referring to Liu, S. et al. Syntheis [synthesis] (2001), 14,2078 and Kompella, A. et al. Org.Proc.Res.Dev. are [organic Working research and exploitation] (2012), 16,1794.This reaction is shown in scheme 9.
Scheme 9
Alternatively, (wherein n is 1 to the compound with formula (VII), and X is Cl, Br, I or OSO2Me and Y are Br, I Or CN) it is commercially available, or can be prepared from the compound with formula (XII), by between 0 DEG C and 100 DEG C At a temperature of in suitable solvent (for example, dichloromethane) in triphenylphosphine in the presence of with halogen source (for example, CCl3Br、CCl4 Or I2) carry out processing or with mesyl chloride (ClSO2Me it) is handled.About related example, referring to Liu, H. et al. Bioorg.Med.Chem. [biological organic and pharmaceutical chemistry] (2008), 16,10013, WO 2014/020350 and Kompella, Et al. A. [biological organic and pharmaceutical chemistry bulletin] (2001) Bioorg.Med.Chem.Lett., 1,3161.With formula (XII) Compound be commercially available.This reaction is shown in scheme 10.
Scheme 10
It can be in agricultural sector and related field using the compound with formula (I), as example for controlling plant The active constituent of harmful organism, or using for controlling putrefactive microorganisms or having to people is potentially harmful on non-living material Body.The characteristic of these compounds is that application rate is low but active height, and Plant Tolerance is good and does not endanger environment.They Have highly useful treatment, prevent and systematic speciality and can be used for protecting countless cultivating plants.With formula (I) Compound can be used for inhibiting or destroy plant in a variety of different useful plant crops or plant part (fruit, flower, leaf Son, stem, stem tuber, root) on there is evil biology, while also protect for example later growth those of plant part from cause plant The infringement of the microorganism of object disease.
The invention further relates to (wherein will be effective by handling plant or the cereal crops of plant propagation material and/or harvest The compound with formula (I) of amount is applied to plant, its part or its place) control or prevent plant or plant propagation material And/or easily by the food crops of the harvest of microorganism attack from the method for infringement.
The compound with formula (I) can also be used as fungicide.As used herein, term " fungicide " means The compound for controlling, modifying or preventing fungi from growing.Term " effective fungicidal amount ", which means that fungi can be grown, to be had an impact Such a compound or such compound combination amount.Control or the influence changed include all from developing naturally Deviate, such as kill, block etc., and prevent to be included in barrier or other defence structures that fungal infection is prevented in face in or on plant It makes.
Can also use the compound with formula (I) as processing plant propagation material (for example, seed, as fruit, stem tuber or Cereal) or plant cutting seed dressing, for protect to anti-fungal infection together with confrontation soil in existing plant-pathogenic it is true Bacterium.It can be before plantation with the compositions-treated propagating materials for including the compound with formula (I)：Such as can sowing with Preceding coating seed., by impregnating seed in liquid formulations or by being coated them with solid formulation can also will have The reactive compound of formula (I) is applied to cereal (coating).Composition can also be applied to plantation position when planting propagating materials Point, such as it is applied to during sowing the ditch dug with a plow of seed.The invention further relates to such methods of processing plant propagation material, and And it is related to the plant propagation material so handled.
In addition, the compound with formula (I) can be used for controlling the fungi of related field, the field is for example in industry In the protection of material (including timber and industrial products related with timber), food storage in, in administration of health.
It is also possible to for protecting non-living material (such as timber, wallboard and coating) from fungal attack.
Compound with Formulas I is for example for the fungi of disease and fungal vector and phytopathogenic bacterium and virus Effectively.The fungi of these diseases and fungal vector and plant-pathogenic bacterium and virus are for example：
Umbrella branch pears head is mould, Alternaria species, Aphanomyces species, Ascochyta species, Aspergillus sp are (including yellow bent Mould, aspergillus fumigatus, aspergillus nidulans, aspergillus niger, Aspergillus terreus), Aureobasidium species (including Aureobasidium pullulans (A.pullulans)), Blastomyces dermatitidis, wheat powdery mildew, lettuce disk obstruct mould (Bremia lactucae), Botryosphaeria species (including grape Ulcer bacteria (B.dothidea), tree flower lichens grape seat chamber bacterium (B.obtusa)), Botrytis species (including Botrytis cinerea (B.cinerea)), Candida species (including Candida albicans, smooth ball candida albicans (C.glabrata), Cruise beads Bacterium (C.krusei), grape tooth candida albicans (C.lusitaniae), Candida parapsilosis (C.parapsilosis), Candida tropicalis (C.tropicalis)), Cephaloascus fragrans, long beak shell species, Cercospora species (including brown patch germ (C.arachidicola)), late pinta bacterium (Cercosporidium personatum), Cladosporium species, ergot, thick Coccidioides immitis, cochliobolus species, colletotrichum species (including Glorosprium musarum Cookeet Mass (C.musae)), Cryptococcus neoformans, Seat shell category (Diaporthe) species, Asia are every spore shell species, Drechslera species, Elsinochrome species, Epidermophyton Species, erwinia amylovora, Erysiphe species (including composite family powdery mildew (E.cichoracearum)), eutypa dieback bacterium (Eutypa lata), Fusarium species (including fusarium culmorum, Fusarium graminearum, F.langsethiae, beading reaping hook Bacterium, glue fusarium oxysporum, Fusarinm solani, Fusarium oxysporum, fusarium prolifertum), gaeumannomyces graminis (Gaeumannomyces Graminis), Gibberella fujikuroi (Gibberella fujikuroi), coal smoke germ (Gloeodes pomigena), banana charcoal The long spore bacterium of subcutaneous ulcer disk (Gloeosporium musarum), apple anthrax bacteria (Glomerella cingulate), grape ball seat Bacterium (Guignardia bidwellii), plant are by Chinese juniper glue rest fungus (Gymnosporangium juniperi- Virginianae), Helminthosporium species, camel spore rest fungus species, Histoplasma species (including Histoplasma capsulatum (H.capsulatum)), red line germ, Leptographium lindbergi, pepper powdery mildew bacterium (Leveillula Taurica), pine needle dissipate disk shell (Lophodermium seditiosum), the mould withered bacterium of leaf (Microdochium nivale) of snow, Microsporium species, chain sclerotinia sclerotiorum species, Mucor species, mycosphaerella species (including standing grain green-ball chamber bacterium, apple stain Germ (M.pomi)), treetop blight bacterium, dragon spruce germ, Paracoccidioides species, Penicillium spp (including Penicillium digitatum, meaning Big profit mould), Petriellidium species, referring to downy mildew species, (including Peronosclerospora maydis, Philippine's frost refer to mould and sorghum and refer to frost It is mould), downy mildew species, phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus Sanghuang (Phellinus igniarus), bottle Mould ant species, Phoma species, grape life plan stem point bacterium (Phomopsis viticola), phytophthora species (including Phytophthora infestans), Plasmopara species (including Plasmopara Halstedll bacterium, Plasmopara viticola (P.viticola)), lattice spore chamber Ella species, Podosphaera species (including white cross hair list softgel shell (P.leucotricha)), Polymyxa Graminis (Polymyxa graminis), Polymyxa betae (Polymyxa betae), wheat Phyllostachys pubescens (Pseudocercosporella herpotrichoides), pseudomonad species, Pseudoperonospora species (including cucumber cream Mildew bacterium, humulus grass vacation downy mildew), Pseudopeziza tracheiphila, downy mildew species (including barley handle rest fungus (P.hordei), wheat leaf rust germ (P.recondita), bar shaped handle rest fungus (P.Striiformis), the brown rest fungus of wheat (P.triticina)) Sclerotinia species, Pyrenophora species, Pyricularia Sacc. species (including Pyricularia oryzae, are buried (P.oryzae)), pythium species (including Pythium ultimum bacterium), Ramularia species, Rhizoctonia species, Rhizomucor pusillus (Rhizomucor pusillus), Rhizopus arrhizus, beak genuss species, trichosporon spp species (including Scedosporium apiospermum and more Educate the more pityrosporion ovales of match), coal point sick (Schizothyrium pomi), Sclerotinia species, sclerotium species, Septoria object Kind (including phaeosphaeria nodorum (S.nodorum), wheat septoria (S.tritici)), strawberry powdery mildew (Sphaerotheca Macularis), monofilament list softgel shell (Sphaerotheca fusca) (cucumber powdery mildew's pathogen (Sphaerotheca Fuliginea)), Sporothrix (Sporothorix) species, many spores of clever withered shell (Stagonospora nodorum), handle of crawling Mould category (Stemphylium) species, hair Boreostereum vibrans (Stereum hirsutum), the withered line germ (Thanatephorus of rice Cucumeris), thielaviopsis sp (Thielaviopsis basicola), Tilletia foetida species, trichoderma species (including breathe out Thatch trichoderma), trichoderma pseudokiningii, Trichoderma viride), trichophyton species, core coral Pseudomonas species, grape snag shell, Urocystis (Urocystis) species, Ustilago (Ustilago) species, Venturia species (including venturia inaequalis (V.inaequalis)), Verticillium sp and Xanthomonas campestris species.
Compound with formula (I) can be used for such as lawn, ornamental plant such as flowers, shrub, broadleaf tree or evergreen Plant, such as coniferals and trees injection, pest management etc..
Within the scope of the invention, target crop to be protected and/or useful plant typically comprise perennial and one Annual crop, such as Berry plant, such as blackberry, blueberry, blueberry, Cranberry, raspberry and strawberry；Cereal, such as barley, corn (maize, corn), millet, oat, rice, rye, sorghum, triticale and wheat；Fibre plant, for example, cotton, flax, Hemp, jute and sisal hemp；Field crop, such as sugar beet and fodder beet, coffee bean, hops, leaf mustard, rape (Kano Draw), opium poppy, sugarcane, sunflower, tea and tobacco；Fruit tree, for example, apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, Pears and plum；Grass, for example, Bermuda grass, bluegrass, this spy grass, ciliate desert-grass, fescue, rye grass, saint augustine grass and Korea lawn grass；Medicinal herbs, as sweet basil, Common Borage, chives, coriandrum, lavender, Lovage, peppermint, wild marjoram, caraway, rosemary, Salvia japonica and thyme；Beans, such as Kidney bean, lens, pea and soybean；Nut, for example, almond, cashew nut, peanut, Fibert, peanut, hickory nut, American pistachios and walnut；Palm plant, such as oil palm；Ornamental plant, for example, flowers, shrub and Tree；Other trees, such as cocoa, coconut, olive and rubber；Vegetables, such as asparagus, eggplant, broccoli, cabbage, Hu Luo Fore-telling, cucumber, garlic, lettuce, cucurbita pepo, muskmelon, gumbo, onion, pepper, potato, pumpkin, rheum officinale, spinach and tomato；With And grapevine, such as grape.
Term " useful plant " should be understood as further including since conventional breeding methods or genetic engineering cause it to weeding Agent (as Bromoxynil) or classes of herbicides (such as HPPD inhibitor, ALS inhibitor, such as primisulfuronmethyl, the third sulphur of fluorine is grand and trifluoro Pyridine sulphur is grand, EPSPS (5- enol-acetone-shikimic acid -3- phosphoric acid-synzyme) inhibitor, GS (glutamine synthelase) inhibitor Or PPO (proporphyrinogen oxidase) inhibitor) tolerance useful plant.Caused to miaow by conventional breeding methods (mutagenesis) The example of crop of oxazoline ketone (such as imazamox) tolerance isSummer rape (Canola).Pass through Gene engineering method causes the example for the crop being resistant to herbicide or classes of herbicides to include glyphosate and glufosinate-resistant corn Kind, theyHerculex I andIt is commercially available under trade (brand) name.
Term " useful plant " should be understood as further including having made it by such conversion by using recombinant DNA technology The useful plant of one or more selectively acting toxin can be synthesized, these toxin are that for example to come from toxin producing thin as known Bacterium, especially those of bacillus bacterium.
The example of such plant is：YieldGard (corn variety expresses CryIA (b) toxin)；YieldGard Rootworm (corn variety expresses CryIIIB (b1) toxin)；YieldGard Plus (corn variety, expression CryIA (b) and CryIIIB (b1) toxin)；Starlink (corn variety expresses Cry9 (c) toxin)；Herculex I (corn variety, expression The enzyme phosphinothricin N-acetyl transferase (PAT) of salt drug resistance is pressed herbicide glufosinate-ammonium in CryIF (a2) toxin and acquisition)； NuCOTN 33B (cotton variety expresses CryIA (c) toxin)；Bollgard I (cotton variety expresses CryIA (c) toxin)； Bollgard(cotton variety, expression CryIA (c) and CryIIA (b) toxin)；VIPCOT (cotton variety, expression VIP poison Element)；NewLeaf (Potato Cultivars, expression CryIIIA toxin)；NatureGardGT Advantage(GA21 Glyphosate tolerant character),CB Advantage (Bt11 corn borers (CB) character),RW (corn rootworms Character) and Protecta.
Term " crop " should be understood as further including by using recombinant DNA technology and by conversion can in this way The crop plants of one or more selectively acting toxin are synthesized, these toxin are for example to come from toxin producing bacterium as known, Especially those of bacillus bacterium.
The toxin of Expressed in Transgenic Plant that can be in this way includes for example from bacillus cereus or Japanese beetle The insecticidal proteins of bacillus；Or the insecticidal proteins from bacillus thuringiensis, such as delta-endotoxin, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C or Vegetative Insecticidal Proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A；Or the insecticidal proteins of nematosis bacterium, such as Photorhabdus or Xenorhabdus, Such as shine light rod bacterium, Xenorhabdus nematophilus；By animal generate toxin, as scorpion toxin, spider toxin, wasp toxin and its His insect-specific neurotoxin；By mycetogenetic toxin, such as strepto- verticillium toxin；Phytolectin, such as pisum sativum agglutinin, greatly Wheat agglutinin or snowdrop lectin；Pleurotus Ostreatus；Protease inhibitors, as trypsin inhibitor, serine protease press down Preparation, potato storage protein (patatin), cystatin, antipain；RIP activity Albumen (RIP), as ricin, corn-RIP, abrin, Luffin, Saponaria officinalis toxin protein or different strain are rushed down Root toxalbumin；Steroid metabolism enzyme, such as 3-- hydroxy steroids oxidizing ferment, ecdysteroid-UDP- glycosyls-transferase, cholesterol Oxidizing ferment, moulting hormone inhibitor, HMG-COA- reductases；Ion channel blocking agent, such as sodium channel or calcium channel blocker；It protects Young hormone esterase, diuretic hormone receptor, Stilbene synthase, bibenzyl synthases, chitinase and dextranase.
Further, in the context of the present invention, delta-endotoxin (such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or Vegetative Insecticidal Proteins (Vip) (such as Vip1, Vip2, Vip3 or Vip3A) It is interpreted as obviously further including mixed type toxin, truncated toxin and modified toxin.Mixed type toxin is by those eggs (see, for example, the WO 02/15701) that the Combination nova recombination of white different structure territory generates.Truncated toxin, for example, it is truncated Cry1Ab is known.In the case of modified toxin, one or more amino acid of naturally occurring toxin are replaced. In this amino acid replacement, preferably non-naturally occurring protease recognition sequence is inserted into toxin, such as in Cry3A055 In the case of, a kind of cathepsin-G- identification sequence is inserted into Cry3A toxin (referring to WO 03/018810).
Such toxin or the example of genetically modified plants that can synthesize such toxin are disclosed in such as EP-A-0 374 753, in WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The method for being used to prepare such genetically modified plants is generally known to those skilled in the art and describes in example In publication as mentioned above.CryI types DNA and its preparation are for example from WO 95/34656, EP-A-0 367 474, known in EP-A-0 401 979 and WO 90/13651.
Plant is made to have tolerance to harmful insect including toxin in transgenic plants.These insects can reside in Any classification of insect group, but be especially that typically in beetle (coleoptera), dipteran (Diptera) and butterfly (Lepidoptera) It was found that.
Including the one or more encoding insecticidal agent resistances and transgenosis of the gene of expressing one or more toxin is planted Object be it is known and it is some of be commercially available.The example of such plant is：YieldGard (corn variety, expression Cry1Ab toxin)；YieldGard Rootworm (corn variety, expression Cry3Bb1 toxin)；YieldGard Plus (corns Kind, expression Cry1Ab and Cry3Bb1 toxin)；Starlink (corn variety, expression Cry9C toxin)；Herculex I are (beautiful Herbicide glufosinate-ammonium is shifted in rice kind, expression Cry1Fa2 toxin and acquisition by the enzyme phosphinothricin N-acetyl of salt drug resistance Enzyme (PAT))；NuCOTN 33B (cotton variety, expression Cry1Ac toxin)；Bollgard I (cotton variety, expression Cry1Ac poison Element)；Bollgard(cotton variety, expression Cry1Ac and Cry2Ab toxin)；VipCot (cotton variety, expression Vip3A and Cry1Ab toxin)；NewLeaf (Potato Cultivars, expression Cry3A toxin)；NatureGard、GT Advantage (GA21 glyphosate tolerants character),CB Advantage (Bt11 corn borers (CB) character) and Protecta。
Other examples of such genetically modified crops are：
1.Bt176 corns come from Syngenta seed company (Syngenta Seeds SAS), Huo Bitelu (Chemin de L ' Hobit) 27, F-31790 Sheng Suweier (St.Sauveur), France, registration number C/FR/96/05/10.The jade of genetic modification Chinese sorghum makes it to resist invading for European corn borer (corn borer and powder stems moth) by the truncated Cry1Ab toxin of transgene expression It attacks.Bt11 corns also transgene expression enzyme PAT is to obtain the tolerance to herbicide glufosinate ammonium.
2.Bt11 corns come from Syngenta seed company (Syngenta Seeds SAS), Huo Bitelu (Chemin de L ' Hobit) 27, F-31,790 Sheng Suweier (St.Sauveur), France, registration number C/FR/96/05/10.The jade of genetic modification Chinese sorghum makes it the invasion for resisting European corn borer (corn borer and powder stems moth) by transgene expression Cry1Ab toxin. Bt176 corns also transgene expression PAT enzymes are to obtain the tolerance to herbicide glufosinate ammonium.
3.Bt176 corns come from Syngenta seed company (Syngenta Seeds SAS), Huo Bitelu (Chemin de L ' Hobit) 27, F-31,790 Sheng Suweier (St.Sauveur), France, registration number C/FR/96/05/10.Pass through transgenosis table Up to modified Cry3A toxin with the corn of insect-resistant.This toxin is by being inserted into cathepsin-G- protease Identify sequence and modified Cry3A055.The preparation of such rotaring gene corn plant is described in WO 03/018810.
863 corns of 4.MON come from Monsanto Europe S.A. [Monsanto Europe], 270-272 Avenue De Tervuren [Telford Boulevard], B-1150 Brussels, Belgium [Brussels, Belgium], registration number C/DE/ 02/9.MON 863 expresses Cry3Bb1 toxin, and resistant to certain coleopterons.
531 cottons of 5.IPC come from Monsanto Europe S.A. [Monsanto Europe], 270-272Avenue De Tervuren [Telford Boulevard], B-1150Brussels, Belgium [Brussels, Belgium], registration number C/ES/ 96/02。
6.1507 corns come from Pioneer Overseas Corporation [Pioneer overseas corporation], Avenue Tedesco [Tisco Avenue], 7B-1160 Brussels, Belgium [Brussels, Belgium], registration number C/NL/ 00/10.Genetically altered corn, protein C ry1F is to obtain the resistance to certain lepidopterous insects for expression, and expresses PAT Protein is to obtain the tolerance to herbicide glufosinate ammonium.
810 corns of 7.NK603 × MON come from Monsanto Europe S.A. [Monsanto Europe], 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium [Telford Boulevard, the Brussels B-1150, Belgium], Registration number C/GB/02/M3/03.It is beautiful by the hybridization of conventional breeding by hybridizing the kind NK603 and MON 810 of genetic modification Rice kind is constituted.Express protein C P4 obtained from Agrobacterium strain CP4 to 810 corn genes of NK603 × MON EPSPS is allowed to herbicide-resistant(containing glyphosate), and obtained by Bacillus thuringiensis Kurztaci subsp The Cry1Ab toxin obtained, is allowed to resistance to certain lepidopterous insects, including European corn borer.
Term " place " as used herein means the seed in the place or cultivated plant that plant grows in or on which The place that the place sowed or seed will be placed in the soil.It includes soil, seed and seedling, together with foundation Vegetation.
Term " plant " refers to all tangible parts of plant, including seed, seedlings or saplings, root, stem tuber, stem, stalk, leaf And fruit.
Term " plant propagation material " it should be understood that the reproductive part of plant, such as seed, these parts can be with Breeding for the plant and nutritive material, such as cutting or stem tuber (such as potato).It can be mentioned that such as seed (in a strict sense), root, fruit, stem tuber, bulb, rhizome and the part of plant.It can also refer to after germination or break ground After will be transplanted germinating plants and young plant.These young plants can with complete or partial treatment by dipping and It is protected before transplanting.Preferably, " plant propagation material " it should be understood that seed.
Compound with Formulas I can use in unmodified form, or preferably, routinely be used with preparation field Adjuvant be used together.For this purpose, the paste that they can advantageously be formulated as emulsifiable concentrate in a known manner, can be coated Agent, directly sprayable or dilutable solution or suspension, diluting emulsion, wettable powder, soluble powder, dust agent, Grain and also encapsulant, such as in the substance of polymer.For the type of these compositions, according to expected purpose and Prevailing conditions select method of administration, such as sprinkling, atomization, dusting, send out, are coated or topple over.These compositions can also contain There is other adjuvant, as stabilizer, antifoaming agent, viscosity modifier, adhesive or tackifier and fertilizer, micronutrient supply Body or other be used to obtain the preparation of special-effect.
Suitable carrier and adjuvant (such as agricultural use) can be solid or liquid and be in preparation Useful substance in technology, for example, it is natural or regenerated mineral materials, solvent, dispersion, wetting agent, tackifier, thickener, viscous Mixture or fertilizer.Such as such carrier is described in WO 97/33890.
Suspension-concentrates are that the solid particle of the high degree of dispersion of reactive compound is suspended in aqueous preparation therein.This The preparation of sample includes antisettling agent and dispersant, and may further include wetting agent, to enhance activity and antifoaming agent And crystal growth inhibitor.When in use, in water by the dilution of these concentrates, it and is applied to and needs usually as spray The region of processing.The range of the amount of active constituent can be from 0.5% to the 95% of the concentrate.
Wettable powder is the particle form in easily dispersible high degree of dispersion in water or in other liquid carriers.This A little particles include the active constituent being stored in solid matrix.Typical solid matrix include bleaching earth, kaolin, silica and its He is easy the organic or inorganic solid of humidifying.Wettable powder usually contains the active constituent from 5% to 95% and adds on a small quantity Wetting agent, dispersant or emulsifier.
Emulsifiable concentrate is dispersible uniform liquid composition and can be complete in water or in other liquid It is made of entirely reactive compound and liquid or solid emulsifier, or liquid carrier can also be contained, such as dimethylbenzene, weight aromatics stone Cerebrol, isophorone and other non-volatile organic solvents.When in use, these concentrates are dispersed in water or other liquid In, and it is applied to pending region usually as spray.The range of the amount of active constituent can be from the concentrate 0.5% to 95%.
Granular formulation includes extrudate and compared with both coarse granules, and does not have to usually dilutedly be applied to be treated Region.Typical carriers for granular formulation include sand, bleaching earth, Concave-convex clay rod, bentonite, montmorillonite, vermiculite, treasure Zhu Yan, calcium carbonate, brick, float stone, pyrophyllite, kaolin, dolomite, plaster, wood powder, corncob particles, grating peanut shell, sugar, chlorine Change sodium, sodium sulphate, sodium metasilicate, Boratex, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, ice crystal, stone Cream, diatomite, calcium sulfate and other organic or inorganics absorption reactive compound or be activated the material for closing object coating. Grain preparation usually contain 5% to 25% active component, these ingredients may include surfactant such as heavy aromatics volatile oil, Kerosene and other petroleum distillates or vegetable oil；And/or sticker such as dextrin, glue or synthetic resin.
Dirt powder agent be active constituent and high degree of dispersion solid (such as talcum, clay, flour and other it is organic with it is inorganic The solid as dispersant and carrier) free flowable mixture.
Micro-capsule is typically the droplet or particle for the active constituent being wrapped in the porous shell of inertia, and the porous shell of the inertia allows The material encased is allowed to escape into environment with controllable rate.The diameter of the droplet of packing is typically 1 micron to 50 microns.Packet The liquid wrapped up in typically constitutes the 50% to 95% of capsules weight and can also include solvent in addition to active compounds.Packing Particle be typically porous particle, wherein perforated membrane is by particle orifice sealing, to which reactive specy to be stored in liquid form Inside particle hole.The range of the diameter of particle is typically from 1 millimeter to 1 centimetre and preferably 1 millimeter to 2 millimeters.Particle It is formed by extrusion, cohesion or balling-up or naturally occurring.The example of such material is vermiculite, sintered clay, kaolinite Soil, Concave-convex clay rod, sawdust and granular carbon.Shell or membrane material include natural and synthetic rubber, fibrous material, styrene-fourth Diene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyureas, polyurethane and starch xanthate.
Other useful preparations for agrochemicals application include active constituent solvent (such as acetone, alkylated naphthalene, Dimethylbenzene and other organic solvents) in simple solution, active constituent is completely dissolved with desirable concentration in the solvent. The spray that pressurization can be used, wherein since the evaporation active constituent of low boiling point dispersant solvent carrier is with the shape of high degree of dispersion Formula is disperseed.
It is for preparing the useful suitable agricultural adjuvant and carrier of the composition of the present invention in above-mentioned formulation type Known to one of ordinary skill in the art.
Utilizable liquid carrier includes such as water, toluene, dimethylbenzene, naphtha, crop oil, acetone, Methylethyl Ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, pentyl acetate, 2- butanone, chlorobenzene, hexamethylene, cyclohexanol, alkyl acetate, two Pyruvic alcohol, 1,2- dichloropropanes, diethanol amine, p- diethylbenzene, diethylene glycol (DEG), diethylene glycol abietate, diethylene glycol butyl ether, Diethylene glycol ether, diethylene glycol methyl ether, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO) ,-dioxane of Isosorbide-5-Nitrae, dipropylene glycol, dipropyl two Alcohol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2- ethyl hexyls Alcohol, ethylene carbonate, 1,1,1- trichloroethanes, 2-HEPTANONE, australene, d- limonenes, ethylene glycol, butyl glycol ether, ethylene glycol first Ether, gamma-butyrolacton, glycerine, glycerin diacetate, monoacetin, glycerol triacetate, hexadecane, hexylene glycol, acetic acid are different Pentyl ester, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, lauryl amine, isopropylidene third Ketone, methoxypropanol, methyl isoamyl ketone, methyl iso-butyl ketone (MIBK), methyl laurate, methyl caprylate, methyl oleate, dichloromethane, Meta-xylene, n-hexane, n-octyl amine, stearic acid, acetic acid octylame ester, oleic acid, oleyl amine, ortho-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, paraxylene, toluene, triethyl phosphate, triethylene glycol, xylene monosulfonic acid, Paraffin, mineral oil, trichloro ethylene, perchloroethylene, ethyl acetate, pentyl acetate, butyl acetate, methanol, ethyl alcohol, isopropanol, with And alcohols of higher molecular weight such as amylalcohol, tetrahydrofurfuryl alcohol, hexanol, octanol etc., ethylene glycol, propylene glycol, glycerine and N- methyl -2- Pyrrolidones.Water is typically to dilute the selection carrier of concentrate.
Suitable solid carrier includes such as talcum, titanium dioxide, pyrophillite clay, silica, Concave-convex clay rod, diatom Native (kieselguhr), chalk, diatomite (diatomaxeous earth), lime, calcium carbonate, bentonite, bleaching earth, cotton seed Shell, wheat flour, soy meal, float stone, wood powder, walnut shell powder and lignin.
Can be advantageously with extensive surfactant in the liquid and solid composite, being especially designed to can Before administration with those of carrier dilution.These reagents when in use usually by weight composition preparation from 0.1% to 15%.They can be anion in nature, it is cationic, non-ionic or polymerization and can be used as emulsifier, Wetting agent, suspending agent are used with other purposes.Typical surfactant includes alkyl sulfate such as lauryl sulfate two Ethyl alcohol ammonium；Alkylaryl sulfonates, such as calcium dodecyl benzene sulfonate；Alkyl phenol-alkylene oxide addition products, such as ethoxylated nonyl Phenol-C18；Alcohol-alkylene oxide addition products, such as ethoxylated tridecyl alcohol-C16；Soap, such as odium stearate；Alkylnaphthalene sulfonate, Such as nekal；The salt of dialkyl sulphosuccinate, such as two (2- ethylhexyls) sodium sulfo-succinates；Sorbose Alcohol ester, such as Oleate；Quaternary ammonium, such as lauryl trimethyl ammonium chloride；The polyoxyethylene ester of aliphatic acid, such as poly- second two Alcohol stearate；The block copolymer of ethylene oxide and propylene oxide；And the salt of mono phosphoric acid ester and dialkyl ester.
Other adjuvants usually used in Pestcidal compositions include crystallization inhibitor, viscosity modifier, suspending agent, Spray droplet modifying agent, pigment, antioxidant, foaming agent, antifoaming agent, opacifier, compatibilizing agent, antifoaming agent, screening agent, in With agent and buffer, corrosion inhibitor, dyestuff, flavoring agent, spreading agent, penetrant, micronutrient, emollients, lubricant And sticking agent.
In addition, further, the active constituent or composition of other biocidals can with the combination of compositions of the present invention, and And it is applied in the method for the present invention and at the same time ground or sequentially as the composition of the present invention.When being administered simultaneously, this A little other active constituents can be prepared or be mixed in such as aerosol can together with the composition of the present invention.These are other The active constituent of biocidal can be fungicide, herbicide, insecticide, bactericide, acaricide, nematicide and/or Plant growth regulator.
The pesticides using its popular name being mentioned above are known, for example, from " The Pesticide Manual [pesticides handbook] ", the 15th edition, the Britain crop protection committee (British Crop Protection Council)2009。
In addition, the composition of the present invention can also (" SAR " be induced with one or more systemic acquired resistance derivants Agent) it applies together.SAR derivants are known and are described in such as U.S. Patent number US 6,919,298, and include Such as salicylate and the SAR derivants of commercialization my acid benzene-S-methyls.
Compound with formula (I) is used usually in the form of agrochemical composition and can be with other compound Simultaneously or sequentially it is applied to crop area or pending crop.For example, these other compounds can be influenced The fertilizer or micronutrient donors or other preparations of plant growth.They can also be selective herbicide or non-selective remove Careless agent, together with the mixing of insecticide, fungicide, bactericide, nematicide, invertebrate poison or these several preparations Object, if desired with other carrier usually used in preparation field, surfactant or the adjuvant for promoting application Together.
Compound with formula (I) can be by control or (antifungal) combination of protection confrontation phytopathogenic microorganisms The form of object uses, and the composition includes at least one compound or at least one preferred such as this paper institutes with formula (I) The individual compound of definition is as active constituent (in free form or in the agrochemicals available salt form) and above-mentioned At least one of adjuvant.
Therefore, the present invention provides comprising at least one compound with formula (I), agriculturally acceptable carrier and appoint The composition of selection of land adjuvant, preferably Fungicidal composition.Agriculturally acceptable carrier is the carrier of for example suitable agricultural use. What agricultural carrier was well-known in the art.Preferably, in addition to including the compound with formula (I), the composition may include It is at least one or more of to kill harmful organism reactive compound, such as other Fungicidal active ingredient.
Compound with formula (I) can be the sole active agent of composition, or it is appropriate when it can with it is a kind of or A variety of other active constituents (such as pesticides, fungicide, synergist, herbicide or plant growth regulator) are mixed It closes.In some cases, active constituent in addition can lead to unexpected synergistic activity.
The example of other active constituent appropriate includes following item：Non-cyclic amino acids (acycloamino acid) kill very Microbial inoculum, aliphatic nitrogen fungicide, amide fungicides, aniline fungicide, antibiotic fungicide, aromatic series are antifungal Agent, fungicide containing arsenic, aryl phenyl one fungicide, benzamide fungicide, benzanilide fungicide, benzo miaow Azoles fungicide, benzthiazole fungicides, plant fungicide, bridged biphenyls base fungicide, carbamate are antifungal Agent, phenylamino formic acid esters fungicide, health azoles fungicide, copper fungicide, dicarboximide fungicide, dinitrophenol kill Epiphyte pharmaceutical, dithiocarbamate fungicide, dithiolane fungicide, furoamide fungicide, chaff aniline are antifungal Agent, hydrazides epiphyte pharmaceutical, imidazole fungicides, mercury fungicide, morpholine fungicide, organophosphorus insecticidal epiphyte pharmaceutical, organotin kill very Microbial inoculum, oxathiin (oxathiin) fungicide, oxazoles fungicide, benzenesulfonamide fungicide, polysulfide Fungicide, pyrazoles fungicide, pyridine fungicide, pyrimidine fungicide, pyrroles's fungicide, quaternary ammonium fungicide, quinoline Fungicide, quinone fungicide, quinoxaline fungicide, strobilurin fungicide, sulfonanilide (sulfonanilide) Fungicide, thiadiazoles fungicide, thiazole fungicide, thiazolidine fungicide, thiocarbamate fungicides, thiophene Pheno fungicide, triazine fungicide, triazole antifungal agents, triazolo pyrimidine fungicide, urea fungicide, valine amide (valinamide) fungicide and zinc fungicide.
The example of other active constituent appropriate further includes following item：3- difluoromethyl -1- methyl-1 H- pyrazoles -4- first Sour (9- dichloromethylenes -1,2,3,4- tetrahydrochysenes-Isosorbide-5-Nitrae-methylene-naphthalene -5- bases)-amide, 3- difluoromethyl -1- methyl-1 H- pyrroles Azoles -4- carboxylic acid methoxies-[1- methyl -2- (2,4,6- trichlorophenyl)-ethyl]-amide, 1- methyl -3- difluoromethyl -1H- pyrroles Azoles -4- formic acid (2- dichloromethylene -3- ethyls -1- methyl-indane -4- bases)-amide (1072957-71-1), 1- methyl -3- Difluoromethyl -1H- pyrazoles -4- formic acid (4 '-methanesulfonyl-biphenyl -2- bases)-amide, 1- methyl -3- difluoromethyls -4H- Pyrazoles -4- formic acid [2- (2,4- Dichloro-phenyl) -2- methoxyl group -1- methyl-ethyls]-amide, (chloro- 2, the 4- dimethyl-pyrroles of 5- Pyridine -3- bases)-(2,3,4- trimethoxy -6- methylphenyls)-ketone, (the chloro- 2- methoxv-pyridines -3- bases of the bromo- 4- of 5-)-(2, 3,4- trimethoxy -6- methylphenyls)-ketone, 2- { 2- [(E) -3- (2,6- Dichloro-phenyl) -1- methyl -propyl- 2- alkene - (E)-yldeneamino oxygroup methyl]-phenyl -2- [(Z)-methoxyimino]-N- methyl acetamides, 3- [5- (the chloro- benzene of 4- Base)-isoxazole alkyl -3- bases of -2,3- dimethyl]-pyridine, (E)-N- methyl -2- [2- (2,5- Dimethylphenoxymethyl) benzene Base] -2- methoxyl groups-imido yl acetamide, bromo- 2- cyano-N, N- dimethyl -6- trifluoro methyl benzimidazole-the 1- sulfanilamide (SN) of 4-, a- [N- (chloro- 2, the 6- xylyls of 3-) -2- methoxyl acetamides base]-y- butyrolactone, the chloro- 2- cyano-N of 4-, -5- pairs of-dimethyl Tolylimidazol -1- sulfanilamide (SN), N- allyls -4,5,-dimethyl -2- trimethyl silyl thiophene -3- formamides, N- (1- cyanogen Base -1,2- dimethyl propyl) -2- (2,4- dichlorophenoxy) propionamide, N- (2- methoxyl group -5- pyridyl groups)-cyclopropanecarbonyl Amine, (.+-.)-cis- -1- (4- chlorphenyls) -2- (1H-1,2,4- triazol-1-yls)-suberol, 2- (1- tertiary butyls) -1- (2- Chlorphenyl) -3- (1,2,4- triazol-1-yl) -propyl- 2- alcohol, 2 ', 6 '-two bromo- -4 '-fluoroforms of 2- methyl -4- trifluoromethoxies Base -1,3-thiazoles -5- formailides, 1- imidazole radicals -1- (4 '-chlorophenoxy) -3,3- dimethyl butyrate -2- ketone, (E) -2- [2- [6- (2- cyano-benzene oxygens) pyrimidine-4-yl oxygroup] phenyl] 3- methoxy-methyl acrylates, (E) -2- [2- [6- (2- sulfenyl amine Phenoxyl) pyrimidine-4-yl oxygroup] phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [6- (2- fluorophenoxies) pyrimidines - 4- bases oxygroup] phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [6- (2,6- difluoro phenoxy group) pyrimidine-4-yl oxygroup] Phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [3- (pyrimidine-2-yloxy) phenoxy group] phenyl] -3- methoxyl group propylene Sour methyl esters, (E) -2- [2- [3- (5- methylpyrimidine -2- bases oxygroup)-phenoxy group] phenyl] -3- methoxy-methyl acrylates, (E) - 2- [2- [3- (phenyl-sulfonyl oxygroup) phenoxy group] phenyl -3- methoxy-methyl acrylates, (E) -2- [2- [3- (4- nitrobenzenes Oxygroup) phenoxy group] phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- Phenoxyphenyls] -3- methoxy-methyl acrylates, (E) -2- [2- (3,5- Dimethyl-benzoyl) pyrroles -1- bases] -3- methoxy-methyl acrylates, (E) -2- [2- (3- methoxies Phenoxyl) phenyl] -3- methoxy-methyl acrylates, (E) -2 [2- (2- phenylethylene -1- bases)-phenyl] -3- methoxy propyls E pioic acid methyl ester, (E) -2- [2- (3,5- dichlorophenoxy) pyridin-3-yl] -3- methoxy-methyl acrylates, (E) -2- (2- (3- (1,1,2,2- tetrafluoro ethyoxyl) phenoxy group) phenyl) -3- methoxy-methyl acrylates, (E) -2- (2- [3- (Alpha-hydroxy benzyl) Phenoxy group] phenyl) -3- methoxy-methyl acrylates, (E) -2- (2- (4- phenoxypyridines -2- bases oxygroup) phenyl) -3- methoxies Base methyl acrylate, (E) -2- [2- (3- n-propyls oxygroup-phenoxy group) phenyl] 3- methoxy-methyl acrylates, (E) -2- [2- (3- isopropyl oxygroups phenoxy group) phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [3- (2- fluorophenoxies) phenoxy group] Phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- (3- ethoxy phenoxies) phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- (4- tert-Butyl-pyridin -2- bases oxygroup) phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [3- (3- cyano Phenoxy group) phenoxy group] phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [(3- methvl-pyridinium -2- base oxygroups methyl) benzene Base] -3- methoxy-methyl acrylates, (E) -2- [2- [6- (2- methyl-phenoxvs) pyrimidine-4-yl oxygroup] phenyl] -3- methoxies Base methyl acrylate, (E) -2- [2- (the bromo- pyridine -2- bases oxygroup methyl of 5-) phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- (3- (3- iodine pyridine -2- bases oxygroup) phenoxy group) phenyl] -3- methoxy-methyl acrylates, (E) -2- [2- [6- (2- chlorine pyrroles Pyridine -3- bases oxygroup) pyrimidine-4-yl oxygroup] phenyl] -3- methoxy-methyl acrylates, (E), (E) -2- [2- (5,6- dimethyl pyrazoles Piperazine -2- ylmethyl oximidos methyl) phenyl] -3- methoxy-methyl acrylates, (E) -2- { 2- [6- (6- picoline -2- base oxygen Base) pyrimidine-4-yl oxygroup] phenyl -3- methoxy group-methyl acrylates, (E), (E) -2- { 2- (3- methoxyphenyls) methyloximes Ylmethyl]-phenyl -3- methoxy-methyl acrylates, (E) -2- 2- (6- (2- triazobenzenes oxygroup)-pyrimidine-4-yl oxygroup] Phenyl } -3- methoxy-methyl acrylates, (E), (E) -2- { 2- [6- phenyl pyrimidine -4- bases)-methyloxime ylmethyl] phenyl } -3- Methoxy-methyl acrylate, (E), (E) -2- { 2- [(4- chlorphenyls)-methyloxime ylmethyl]-phenyl } -3- methoxy acrylic acids Methyl esters, (E) -2- { 2- [6- (2- n-propylbenzenes oxygroup) -1,3,5-triazines -4- bases oxygroup] phenyl } -3- methoxy acrylic acid first Ester, (E), (E) -2- { 2- [(3- nitrobenzophenones) methyloxime ylmethyl] phenyl } -3- methoxy-methyl acrylates, the chloro- 7- (2- of 3- Azepine -2,7,7- trimethyls-octyl- 3- alkene -5-ine), 2,6- bis- chloro- N- (4- trifluoromethyl benzyls)-benzamide, the iodo- 2- of 3- Bromo- 2,3-, the bis- iodo- 2- acrylic ethyl carbamates of propilolic alcohol, 4- chlorphenyl -3- iodine propargyls formal, 3-, 2,3,3- Bromo- 2,3-, the bis- iodo- 2- propenyls of triiodo allyl alcohol, 3-, the iodo- 2-propynyl n-butylamino formic acid esters of 3-, the iodo- 2-propynyls of 3- The iodo- 2-propynyl cyclohexyl-carbamate of n-hexyl carbamate, 3-, the iodo- 2-propynyl carbanilates of 3-； Phenol derivatives, such as tribromphenol, tetra-chloro-phenol, 3- methyl -4- chlorophenols, 3,5- dimethyl -4- chlorophenols, Phenoxyethanol, dichloro Phenol, o-phenyl phenol, phenylphenol, p-phenyl phenol, 2- benzyl -4- chlorophenols, 5- hydroxyls -2 (5H)-furanone；4,5- bis- Chlorine dithiazole quinoline ketone, 4,5- benzo dithiazole quinolines ketone, 4,5- trimethylene dithiazole quinolines ketone, chloro- bis- sulphur of (3H) -1,2- of 4,5- bis- Base 1-3- ketone, 3,5- dimethyl-tetrahydros -1,3,5- thiadiazine -2- thioketones, N- (2- is to chlorobenzoyl ethyl)-chlorination hexamethylene Tetramine, Acibenzolar, eight or nine ten nitration mixture (acypetacs), alanycarb, albendazole, cartap (aldimorph), allicin, allyl Alcohol, ametoctradin, amisulbrom, A Muba (amobam), ammonia propyl-phosphine sour (ampropylfos), anilazine, asomate (asomate), aureofungin (aureofungin), azaconazole, A Zhafending (azafendin), azithiram sterilization Agent (azithiram), Fluoxastrobin, barium polysulfide, M 9834, M 9834-M, benodanil (benodanil), benomyl, enemy bacterium Hydrazone, the third azoles grass grand (bentaluron), benzene metsulfovax, benthiozole, benzalkonium chloride, section olefin(e) acid (benzamacril), benzene are miscellaneous (benzamorf), benzyl hydroximic acid, benzo alkene fluorine bacterium azoles (benzovindiflupyr), berberine, hundred kill it is pungent (bethoxazin), Bitertanol (biloxazol), binapacryl, xenyl, bitertanol, bithionol, biphenyl pyrrole Bacterium amine (bixafen), blasticidin S-S, Boscalid, bromothalonil, bromuconazole, bupirimate, buthiobate, butylamine are more Calcium sulfide, difoltan, captan, carbamorph, carbendazim, carbendazim hydrochloride, carboxin, plus general amine, carvol, CGA41396, CGA41397, chinomethionat, chitosan, the trace azoles (chlobenthiazone) that goes out, Imugan, chloranil, chlorine sweet smell azoles, Luxuriant scattered, chloropicrin, Bravo, gram chlorine obtain (chlorozolinate), chlozolinate, Climbazole, clotrimazole, carat health (clozylacon), the compound of cupric such as copper acetate, copper carbonate, Kocide SD, copper naphthenate, copper oleate, COPPER OXYCHLORIDE 37,5, oxygen Base copper 8-hydroxyquinolinate, cupric silicate, copper sulphate, copper resinate, copper chromate zinc and Bordeaux mixture, cresols, cufraneb, cuprobam (cuprobam), cuprous oxide, cyazofamid, ring bacterium amine (cyclafuramid), cycloheximide, cyflufenamid, cymoxanil, Cypendazole (cypendazole), cyproconazole, cyprodinil, dazomet, debacarb, decafentin, dehydroactic acid, two -2- pyridyl groups two 1,1 '-dioxide of sulfide, Euparen (dichlofluanid), diclomezine, dichlone, botran, antiphen, sclerotium Profit, diclobutrazol, double chlorine zarilamid, diethofencarb, difenoconazole, difenzoquat, difluoro woods, O, bis- i-propyl-S- benzyls of O- Thiophosphate, U.S. good fortune azoles (dimefluazole), dimethachlon, Miconazole (dimetconazole), dimethomorph, two The phonetic phenol of first, olefin conversion, olefin conversion-M, dinobuton, dinocap, dinocton-O, dinopenton (dinopenton), nitre monooctyl ester (dinosulfon), dinoterbon (dinoterbon), diphenylamines, Dipyrithione, disulfiram, Plondrel (ditalimfos), two Thiophene agriculture, disulfide group ether, dodecyl dimethyl ammonium chloride, dodemorph, dodicin, dodine, dodine, Drazoxolon, edifenphos, Enestroburin, epoxiconazole, etaconazole, Ethisul (etem), Guardian, ethirimol, ethoxyquin, second garlic Plain (ethilicin), (Z)-N- benzyls-N ([methyl (the thio ethyleneimino-Epoxide carbonyl of methyl -) amino] sulfenyl)-β-ammonia Base ethyl propionate, Grandox fumigant, Famoxate, Fenamidone, Dexon, fenapanil, Fenarimol, benzoxazole, fenfuram, Fenhexamid, kind clothing ester, zarilamid, fenpiclonil, fenpicoxamid, fenpropidin, butadiene morpholine, amine benzene pyrrole bacterium ketone, fentin Acetate, triphenyl tin hydroxide, fervam, ferimzone, fluazinam, fludioxonil, fluorine U.S. support, flumorph, fluopicolide (flupicolide), fluopyram, azoles furan grass, fluotrimazole (fluotrimazole), fluoxastrobin, Fluquinconazole, fluorine silicon Azoles, flusulfamide, flutolanil (flutanil), flutolanil, Flutriafol, fluxapyroxad, folpet, formaldehyde, triethylphosphine acid, the wheat head Rather, furalaxyl, furametpyr, furcarbanil, furconazole, furfural, Mao Gu are happy, furan bacterium is grand, glyoxide, griseofulvin, biguanides are pungent Amine, halacrinate (halacrinate), hexachloro-benzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexamethylene sulphur phosphorus (hexylthiofos), hydrargaphen (hydrargaphen), hydoxyisoxazole, hymexazol, imazalil, Imazalil sulfate, Asia Amine azoles, iminoctadine, iminoctadine triacetate, znezin (inezin), iodo propinyl butyl methylamine acid esters (iodocarb), kind bacterium azoles, ipfentrifluconazole, different rice blast net, iprodione, Propineb, isopropyl butylamino first Acid esters, Isoprothiolane, isopyrazam, isotianil, chlorobenzene Climbazole (isoyaledione), izopamfos (izopamfes), spring Thunder mycin, kresoxim-methyl-methyl, LY186054, LY211795, LY248908, Mancozeb, mandipropamid, maneb, adjacent acyl Amine, miaow card disease western (mecarbinzid), Metalaxyl-M, fluorine chlorine ether bacterium azoles (mefentrifluconazole), mepanipyrim, go out rust Amine, mercury chloride, calogreen, the mite that disappears more (meptyldinocap), metalaxyl, Metalaxyl-M-M, metham-sodium, Jing Cha azolactones (metazoxolon), metconazole, methasulfocarb, methuroxam, methyl bromide, methyl iodide, methyl-isorhodanate, Carbatene, Carbatene- Zinc, SSF 126, metrafenone, metsulfovax, milneb (milneb), moroxydine (moroxydine), nitrile bacterium azoles, myclozolin (myclozolin), Dithane A40 (nabam), Natamycin, neoasozin, Sankel, nitrostyrolene, nitrothalisopropyl, nuarimol, Different thiophene bacterium ketone, ofurace, organomercurial compound class, orysastrobin, Osthole (the white spirits of osthol), Evil, oxasulfuron, Austria Octyl- copper (oxine-copper), oxolinic acid, Ou Baike azoles (oxpoconazole), oxycarboxin, parinol (parinol), Pefurazoate, penconazole, Pencycuron, penflufen-containing, pentachlorophenol, pyrrole metsulfovax, 2-cyano-3-amino-3-phenylancryic acetate, phenazine oxide, phosdiphen (phosdiphen), Yimeiling-Al, phosphoric acid class, phthalide, ZEN 90160, pipron, multiple-amino ester formate, polyoxin D, more Oxygen auspicious not (polyoxrim), Carbatene (polyram), probenazole, Prochloraz, procymidone, propamidine (propamidine), Propamocarb, propiconazole, Propineb, propionic acid, the third oxygen quinoline, prothiocarb (prothiocarb), rosickyite bacterium Azoles, fluorine azoles bacterium acyl azanol (pydiflumetofen), pyracarbolid, pyraclostrobin, azoles amine bacterium ester (pyrametrostrobin), azoles Bacterium ester, Ppyrazophos, pyrrole bacterium benzene prestige, pyridinitril (pyridinitril), pyrifenox, pyrimethanil, pyrrole fragrant ketone difficult to understand (pyriofenone), pyroquilon, pyrrole chlorine clever (pyroxychlor), chlorine pyrrole furan ether, pyrrolnitrin, quaternary ammonium compound, hydroxyl quinoline Quinoline base ethyl ketone (quinacetol), quinazamid (quinazamid), azoles oxolinic acide (quinconazole), chinomethionat, quinoxyfen, Pentachloronitrobenzene, pyrrole imidazoles (rabenzazole), Wormseed plain (santonin), ring benzene pyrrole bacterium amine (sedaxane), silicon thiophene bacterium Amine, simeconazoles, western gram azoles (sipconazole), penta sodium pentachlorophenate, benzo alkene fluorine bacterium azoles (solatenol), volution bacterium amine, strepto- Element, sulphur, sultropen (sultropen), Tebuconazole, isobutyl ethoxyquin (tebfloquin), tecloftalam, tecnazene, Tecoram, fluorine ether azoles, thiabendazolum, thiophene difluoro (thiadifluor), thicyofen (thicyofen), thiophene fluorine bacterium amine, 2- (sulphur Cyanomethylthio) benzothiazole, thiophanate-methyl, Eradex (thioquinox), plug logical sequence, tiadinil, glyoxalin (timibenconazole), sulphur benzonitrile formamide (tioxymid), vertical withered phosphorus-methyl, tolyfluanid, triazolone, triazole Alcohol, triamiphos (triamiphos), triarimol (triarimol), fourth triazole, triazoxide, tricyclazole, tridemorph, trifloxystrobin, Pyridine worm miaow (triflumazole), triforine, fluorine bacterium azoles, triticonazole, uniconazole P, bis methylarsine (urbacide), jinggangmycin, Downy mildew goes out (valifenalate), prestige hundred, vinclozolin, zarilamid (zarilamid), zineb, ziram and benzoyl Bacterium amine.
The compound of the present invention can also be applied in combination with dehelminthization medicament.Such dehelminthization medicament includes being selected from big ring The compound of lactone compound, as ivermectin, avermectin, abamectin, according to mark's fourth, Eprinomectin, Duo Lake Spit of fland, selamectin, Moxidectin, nemadectin and milbemycin derivatives, such as in EP-357460, EP-444964 and Described in EP-594291.Other dehelminthization medicament includes semi-synthetic and biosynthesis avermectin/milbemycin derives Object, as those of described in US-5015630, WO-9415944 and WO-9522552.Other dehelminthization medicament includes benzene And imidazoles, such as albendazole, cambendazole, Fenbendazole, flubendazole, mebendazol, oxfendazole, oxibendazole, Other of Parbendazole and the category member.Other dehelminthization medicament includes Imidazothiazole class and tetrahydropyrimidine class, Such as tetramisole, levamisol, Pyrantel Pamoate, oxantel or Morantel.Other dehelminthization medicament includes killing Fluke agent (such as Triclabendazole and clorsulon) and teniacide (such as praziquantel and epsiprantel).
The compound of the present invention can be with paraherquamides (paraherquamide)/marcfortines (marcfortine) Derivative of class dehelminthization medicament and the like and anti-raw worm oxazoline is posted (such as in US-5478855, US-4639771 and DE- Disclosed in 19520936) it is applied in combination.
The compound of the present invention can be with the general classes dioxo morpholine antiparasitic as described in WO 96/15121 Derivative and the like and also with the cyclic depsipeptide of anthelmintic activity (such as WO 96/11945, WO 93/19053, WO 93/25543, institute in EP 0 626 375, EP 0 382 173, WO 94/19334, EP 0 382 173 and EP 0 503 538 Those of state) be applied in combination.
The compound of the present invention can be applied in combination with other ectoparasiticides；Such as ethiprole；Pyrethroid； Organophosphorus ester；Insect growth regulator, IGR (such as lufenuron)；Moulting hormone agonist (such as tebufenozide)；Anabasine (such as pyrrole worm Quinoline etc.).
The compound of the present invention can be applied in combination with terpenes alkaloids, such as International Patent Application Publication No. WO 95/ Those of described in 19363 or WO 04/72086, the compound especially disclosed in it.
Other examples for the such bioactive compound that can be applied in combination with the compound of the present invention include but not It is limited to following item：
Organophosphorus ester：Orthene, Jia Ji Bi Evil phosphorus, triazotion, methyl azinphos-methyl, bromophos, bromic ether Sulphur phosphorus, cadusafos, four chloroethene phosphorus (chlorethoxyphos), chlopyrifos, Chlorfenvinphos, chlormephos, demeton, demeton-S- first Base, demeton-S- methyl sulfones, dialifos, diazinon, DDVP, Carbicron, Rogor, disulfoton, Ethodan, phonamiphos, Oxygen Diothyl, famphur, fenamiphos, fenifrothion, fensulfothion, Entex, Flupyrazofos-containpesticide, Dyfonate, An Guo, lythidathion, heptan Alkene phosphorus, isazofos, isothioate, karphos, malathion, methacrifos, acephatemet, methidathion, parathion-methyl, Menite, Azodrin, 2-dichloroethylk dimethyl phosphate, omethoate, methyl oxydemeton, paraoxon, parathion, parathion-methyl, phenthoate dimephenthoate cidial, Phosalone, Phosfolan, phosphorus gram, phosmet, phosphamidon, thimet, phoxim, Actellic, Actellic-methyl, Profenofos, Kayaphos, Proetamphos, Toyodan, pyraclofos, pyridaphethione, quinalphos, sulprofos, Temefos, Terbufos, butyl pyrimidine Phosphorus, stirofos, thiometon (thimeton), Hostathion, metrifonate, menazon.
Carbamate：Alanycarb, Aldicarb, 2- 2-phenylbutane vlmethyls formic acid esters, Benfuracard micro, carbaryl, Carbofuran, carbosulfan, worm prestige, ethiofencarb, fenoxycarb, fragrant sulphur gram, furathiocarb, HCN-801, Mobucin, indoxacarb, Mercaptodimethur, methomyl, 5- methyl-m- cumenyl butynyl (methyl) carbamate, oxamyl, Aphox, arprocarb, Thiodicarb, thiofanox, triaguron, UC-51717.
Pyrethroid：Acrinathrin, allethrin, alphamethrin, 5- benzyl -3- furfuryls (E)-(1R) - Cis- -2,2- dimethyl -3- (2- oxo heterocyclic pentane -3- ylidenylmethyls) cyclopropane formic ether, Biphenthrin, β-cyfluthrin ((S)-cyclopenta is different for pyrethroids, cyfloxylate, a- cypermethrins, β-cypermethrin, bioaeroprofen, bioaeroprofen Structure body), bioresmethrin, Biphenthrin, NCI-85193, cycloprothrin, Cyhalothrin, cypermethrin, benzene cyanogen chrysanthemum Ester, decis, Prallethrin, esfenvalerate, ethofenprox, fenfluthrin, Fenpropathrin, fenvalerate, penta chrysanthemum of fluorine cyanogen Ester, flumethrin, taufluvalinate (D isomers), Imiprothrin, Cyhalothrin, λ-gamma cyhalothrin, benzyl chloride Pyrethroids, phenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, θ-chlorine cyanogen chrysanthemum Ester, silafluofene, t- taufluvalinates, Tefluthrin, tralomethrin, ζ-cypermethrin.
Arthropod development conditioning agent：A) chitin synthesis Inhibitors：Benzoyl urea：UC 62644, diflubenzuron, Fluazuron, Flucycloxuron, flufenoxuron, flubenzuron, lufenuron, Rimon, diflubenzuron, desinsection urea, Buprofezin, difenolan, Hexythiazox, second mite Azoles, clofentezine (chlorfentazine)；B) moulting hormone antagonist：Chlorine tebufenozide, methoxyfenozide, tebufenozide；C) children is protected Hormone analogs：Nylar, methoprene (including S- methoprenes), fenoxycarb；D) lipid biosynthesis inhibitors：Envidor.
Other antiparasitic agents：Acequinocyl, Amitraz, AKD-1022, ANS-118, nimbin, Dipel, desinsection Sulphur, Bifenazate, binapacryl, fenisobromolate, BTG-504, BTG-505, toxaphene, cartap, chlorfenethol ester, Spanon, chlorfenapyr, Ring tebufenozide, clothianidin, cyromazine, enemy clone step on (diacloden), methamidophos, DBI-3204, dinactin, two Hydroxyalkyl Ji Jia Ji bis- Hydroxyalkyl bases pyrrolidines, dinobuton, dinocap, 5a,6,9,9a-hexahydro-6,9-methano-2,4, ethiprole, ethofenprox, fenazaquin, flufenzine (flumite), MTI- 800, fenpyroximate, fluacrypyrim, flumethiazide, brofluthrinate, flufenzine, trifluoro, halfenprox (fluproxyfen), halfenprox (halofenprox), hydramethylnon, IKI-220, Kanemite, NC-196, yerba buena careless (neem guard), Buddhist nun oppose Nuo Te Furans (nidinorterfuran), Nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, Pu Luofen Boots (protrifenbute), pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S- 1283, S-1833, SI-8601, silafluofene, silicon Luo Mating (silomadine), pleocidin, tebufenpyrad, tetradiphon, Tetranactin, thiacloprid, thiocyclam, Diacloden, Tolfenpyrad, triaguron, three second pleocidin, trinactin, verbutin, Wave tower rake (vertalec), YI-5301.
Biological agent：Bacillus thuringiensis Ya Shahua subspecies (Bacillus thuringiensis ssp aizawai), Bacillus thuringiensis Kurstaki (kurstaki), bacillus thuringiensis δ endotoxin, baculoviral, Insect Pathogenic Bacterium, virus and fungi.
Bactericide：Aureomycin, terramycin, streptomysin.
Other biological agent：Enrofloxacin, febantel, penethacillin, Meloxicam, cefalexin, kanamycins, not Benzene, clenbuterol, Omeprazole, Tiamulin, benazepil, pyriprole (pyriprole), Cefquinome, Florfenicol, Bu She Rayleigh, cephalo dimension star, Tulathromycin, Ceftiofur, Carprofen, U.S. fluorine hydrazone, praziquantel, Triclabendazole.
Another aspect of the present invention is related to the compound with formula (I) or preferred individual as herein defined Compound, include at least one compound with formula (I) or at least one preferred individual compound as defined above Composition or include at least one compound with formula (I) or at least one preferred as defined above individualized It is antifungal or insecticidal mixtures for controlling to close being mixed with other fungicides as described above or insecticide for object Or prevent the crop of plant (such as useful plant (such as crop plants)), its propagating materials (such as seed), harvest from (such as harvesting Cereal crops) or non-living material from the use that is infected by insect or phytopathogenic microorganisms (preferred fungi organism) On the way.
Another aspect of the present invention relates to control or prevent plant (such as useful plant (such as crop plants)), its breeding material Material (such as seed), the crop (such as cereal crops of harvest) of harvest or non-living material are from by insect or pathogenic Property or putrefactive microorganisms or method that the potentially harmful organism of people (especially fungal organism) is infected, this method includes will Compound with formula (I) or preferred individual compound as defined above as active constituent be applied to these plants, this The part of a little plants or to its place, any part of its propagating materials or these non-living materials.
It controls or prevents to mean by plant-pathogenic or putrefactive microorganisms or to the potentially harmful organism of people (especially very Bacterium organism) reduction of infecting to such a be proved to improved level.
Control or prevent crop plants by the excellent of phytopathogenic microorganisms (especially fungal organism) or infestation by insect Choosing method is foliage applying, and this method, which includes application, has the compound of formula (I) or containing at least one of described compound Agrochemical composition.Frequency of administration and application rate will be depending on the risks by corresponding pathogen or infestation by insect.So And the compound with formula (I) can also be by impregnating the place of the plant with liquid formulations or by that will be in admittedly The compound of body form is for example administered to soil (soil application) and is oozed by root (systemic action) via soil in granular form The saturating plant.In rice crop, such particle can be administered in the rice field poured water.Compound with formula (I) It can also be carried out by impregnating seed or stem tuber with a kind of liquid formulations of fungicide or with a kind of solid formulation It coats and is administered on seed (coating).
A kind of preparation, for example, a kind of compound comprising with formula (I) and (if desired) a kind of solid or Liquid adjuvant or for encapsulate with formula (I) compound monomer composition, can in a known manner, typically via general The compound and extender (such as solvent, solid carrier and, optionally surface active cpd (surfactant)) carry out It nearly mixes and/or grinds to be prepared.
Advantageous application rate is typically active constituent (a.i.)/hectare (ha) from 5g to 2kg, preferably from 10g to 1kg a.i./ha, the most preferably a.i./ha from 20g to 600g.When as seed impregnate reagent in use, suitable dosage is Active material/kg seeds from 10mg to 1g.
When the present invention combination for handle seed when, ratio be 0.001g to 50g have Formulas I compound/kg seeds, The preferably seed from 0.01g to 10g/kg, this is usually enough.
Suitably, preventative (meaning before disease develops) or curative (after meaning that disease develops) application are according to this The composition of the compound with formula (I) of invention.
The composition of the present invention can be used with any conventionally form, for example, with double pack, the pulvis of dry seed treatment (DS), the lotion (ES) of seed treatment, the flowability concentrate (FS) of seed treatment, seed treatment solution (LS), the water-dispersible powder (WS) of seed treatment, the capsule suspension liquid (CF) of seed treatment, seed treatment gel (GF), emulsion concentrates (EC), suspension-concentrates (SC), suspension emulsion (SE), capsule suspension liquid (CS), water-dispersible granule (WG), emulsifiable property particle (EG), water-in-oil emulsion (EO), emulsion oil-in-water (EW), microemulsion (ME), dispersibility oil are outstanding Agent (OD), oil suspending agent (OF), oil-soluble liquor (OL), solubility concentrate (SL), ultra-low volume suspending agent (SU), ultra-low volume Liquor (UL), female medicine (TK), dispersibility concentrate (DC), wettable powder (WP) or with agriculturally acceptable adjuvant combination Any technically feasible preparation form.
Such composition can be produced in a usual manner, such as passes through mixed active ingredient and preparation inert agents appropriate (diluent, solvent, filler and optionally other prepare ingredients, as surfactant, biocide, antifreezing agent, sticker, Thickener and the compound that adjuvanting effect is provided).The conventional extended release preparation for being intended to long-term constant drug effect can also be used.Especially Ground, need with Sprayable (such as water dispersible concentrate (such as EC, SC, DC, OD, SE, EW, EO), wettable powder and Grain) application preparation can contain surfactant (such as wetting agent and dispersant) and provide adjuvanting effect other chemical combination Object, such as formaldehyde and naphthalene sulfonate, alkylaryl sulfonates, lignosulfonates, fatty alkyl sulfate and ethoxylation alkane The condensation product of base phenol and ethoxylized fatty alcohol.
Combination using the present invention and diluent, in the form of suitable seed dressing formulations, such as with to the good of seed Seed dressing formulations are applied to seed by the aqueous suspension or dry powder form of adherence with itself known mode.It is such Seed dressing formulations are known in the art.Seed dressing formulations can be containing encapsulated forms single active ingredient or active constituent Combination, such as spansule or microcapsules.
In general, these preparations include by weight from 0.01% to 90% activating agent, agriculturally may be used from 0 to 20% The surfactant of receiving and 10% to 99.99% solid or liquid preparation of inert agent and one or more adjuvants, the activity Agent by the compound at least with formula (I) optionally with other activating agents (especially microbicide or preservative etc.) together group At.By weight, the conc forms of composition usually contain between about 2% and 80%, preferably between about 5% and 70% Activating agent.By weight, the administration form of preparation can for example containing from 0.01% to 20%, preferably from 0.01% to 5% Activating agent.However commercial product will be preferably formulated as concentrate, end user will be usually using diluted preparation Product.
It is however preferable that being concentrate by commercial product configuration, end user will be usually using diluted preparation Product.
Table 1.1：This table discloses 206 kinds of specific compounds with formula (T-1)：
Wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4, and R1、R2、R3、R4、R5And R6It is hydrogen, and Z is As defined in table 1 below.
Each in table 1.2 to 1.12 (after table 1) makes 206 kinds of individual compounds with formula (T-1) that can obtain, Wherein A1、A2、A3、A4、R1、R2、R3、R4、R5And R6It is such as specifically defined in table 1.2 to 1.12,1 (wherein Z of these table reference tables It is specifically defined).
Table 1
Table 1.2：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R2、R3、R4、R5And R6It is hydrogen, R1It is fluorine, and Z is as defined in upper table 1.
Table 1.3：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R2、R3、R4、R5And R6It is hydrogen, R1It is chlorine, and Z is as defined in upper table 1.
Table 1.4：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R2、R3、R4、R5And R6It is hydrogen, R1It is methyl, and Z is as defined in upper table 1.
Table 1.5：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is N, A2It is C-R2, A3It is C- R3, A4It is C-R4And R2、R3、R4、R5And R6It is hydrogen, and Z is as defined in upper table 1.
Table 1.6：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R1、R2、R4、R5And R6It is hydrogen, R3It is fluorine, and Z is as defined in upper table 1.
Table 1.7：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R2、R4、R5、R6And R7It is hydrogen, R1And R3It is fluorine, and Z is as defined in upper table 1.
Table 1.8：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R3、R4、R5And R6It is hydrogen, R1And R2It is fluorine, and Z is as defined in upper table 1.
Table 1.9：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3It is C-R3, A4It is C-R4And R1、R2、R3、R4And R5It is hydrogen, R6It is methyl, and Z is as defined in upper table 1.
Table 1.10：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3 It is C-R3, A4It is C-R4, and R2、R4And R5It is hydrogen, R3It is fluorine, R6It is methyl, and Z is as defined in upper table 1.
Table 1.11：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3 It is C-R3, A4It is C-R4And R1、R2、R5And R6It is hydrogen, R3And R4It is fluorine, and Z is as defined in upper table 1.
Table 1.12：This table discloses 206 kinds of specific compounds with formula (T-1), wherein A1It is C-R1, A2It is C-R2, A3 It is C-R3, A4It is C-R4And R2、R3、R5And R6It is hydrogen, R1And R4It is fluorine, and Z is as defined in upper table 1.
Example
Next example is used for illustrating the present invention.The difference of the compound of the present invention and known compound can be Under low rate of application the effect of bigger, this can use the experiment journey summarized in instances by those skilled in the art Sequence, using lower rate of application (if necessary) for example, 50ppm, 12.5ppm, 6ppm, 3ppm, 1.5ppm, 0.8ppm or 0.2ppm is confirmed.
Compound with formula (I) especially can include being fought by true for protection plant with any amount of benefit The bioactivity of the advantageous level of microbial disease or for as agricultural chemical active ingredient advantageous characteristic (for example, Higher bioactivity, advantageous activity profile, increased safety (including improved crop tolerance), improved physics-change Learn characteristic or increased biodegradability).
Through this specification, it refers to fusing point to provide temperature and " mp " with degree Celsius (DEG C).LC/MS refers to liquid chromatogram- Mass spectrum, and described device and method (method A, B and C) are described as follows：
The description of LC/MS device and method A is：
SQ detectors 2 from Waters (Waters)
Ioning method：Electrojet
Polarity：Cation and anion
Capillary (kV) 3.0, taper hole (V) 30.00, extractor (V) 2.00, source temperature (DEG C) 150, desolvation temperature (DEG C) 350, taper hole gas flow (L/Hr) 0, dissolve gas flow (L/Hr) 650
Mass range：100 to 900Da
DAD wave-length coverages (nm)：210 to 500.
Method：With the Waters ACQUITY UPLC of following HPLC gradient conditions
(solvent A：20: 1+0.05% formic acid of water/methanol and solvent B：+ 0.05% formic acid of acetonitrile)
Column type：Waters ACQUITY UPLC HSS T3；Column length：30mm；Column internal diameter：2.1mm；Granularity：1.8 micron； Temperature：60℃.
The description of LC/MS device and method B is：
SQ detectors 2 from Waters (Waters)
Ioning method：Electrojet
Polarity：Cation
Capillary (kV) 3.5, taper hole (V) 30.00, extractor (V) 3.00, source temperature (DEG C) 150, desolvation temperature (DEG C) 400, taper hole gas flow (L/Hr) 60, dissolve gas flow (L/Hr) 700
Mass range：140 to 800Da
DAD wave-length coverages (nm)：210 to 400.
Method：With the Waters ACQUITY UPLC of following HPLC gradient conditions
(solvent A：9: 1+0.1% formic acid of water/methanol and solvent B：+ 0.1% formic acid of acetonitrile)
Column type：Waters ACQUITY UPLC HSS T3；Column length：30mm；Column internal diameter：2.1mm；Granularity：1.8 micron； Temperature：60℃.
The description of LC/MS device and method C is：
SQ detectors 2 from Waters (Waters)
Ioning method：Electrojet
H grades of UPLC of mass spectrograph ACQUITY from Waters
Polarity：It converts positive and negative pole
Scan type：MS1 is scanned
Capillary voltage (kV) 3.00, orifice potential (V) 40.00, desolvation temperature (DEG C) 500, taper hole gas flow rate (L/Hr) 50, desolvation gas flow rate (L/Hr) 1000
Mass range：0 to 2000Da
DAD wave-length coverages (nm)：200 to 350.
Method：With the Waters ACQUITY UPLC of following HPLC gradient conditions
(solvent A：+ 0.1% formic acid of water and solvent B：Acetonitrile)
Column type：Waters ACQUITY UPLC BEH C18；Column length：50mm；Column internal diameter：2.1mm；Granularity：1.7 micro- Rice；Temperature：35℃.
If necessary, final compound pure in enantiomter meaning can in due course from racemic material via Standard physical isolation technics (such as reverse phase chiral chromatogram) or by stereoselective syntheses technology (such as by using chirality rise Beginning material) it obtains.
Example of formulation
The active constituent is sufficiently mixed with these adjuvants and is fully ground mixture in suitable grinder, from And provide the wettable powder that can be diluted with water and provide the suspension of desirable concentration.
The active constituent is sufficiently mixed with these adjuvants and is fully ground mixture in grinder appropriate, from And provide the powder for being used directly for seed treatment.
Emulsifiable concentrate
What can be used in plant protection has any required diluted lotion can be by being diluted with water from this It is obtained in kind concentrating agents.
It is used by mixing the active constituent with carrier and grinding mixture in suitable grinder Type dirt powder agent.Such pulvis can be also used for the Waterless Seed Dressing of seed.
Extruder particle
The active constituent is mixed and ground with these adjuvants, and the mixture is soaked with water.Mixture is squeezed Go out and then dries in the air stream.
Packet agriculture granule
Active constituent [compound with formula (I)] 8%
Polyethylene glycol (molecular weight 200) 3%
Kaolin 89%
The active constituent of fine gtinding is uniformly applied in a mixer on the kaolin moistened with polyethylene glycol.With This mode obtains the granule of dustless coating.
Suspension concentrating agents
The active constituent subtly ground is closely mixed with adjuvant, obtains suspension-concentrates, it is dense from the suspension Contracting liquid can obtain the suspension of any desirable dilution by being diluted with water.It, can be to work using such dilution Plant together with plant propagation material carry out handle and it is protected for microbial infection by sprinkling, cast or proofing Shield.
The flowability concentrate of seed treatment
The active constituent subtly ground is closely mixed with adjuvant, obtains suspension-concentrates, it is dense from the suspension Contracting liquid can obtain the suspension of any desirable dilution by being diluted with water.It, can be to work using such dilution Plant together with plant propagation material carry out processing and to its for microbial infection by sprinkling, cast or dipping protect Shield.
The capsule suspension liquid of sustained release
By the combination of 28 parts of the compound with Formulas I and 2 parts of aromatic solvent and 7 parts of toluene diisocynate Ester/polymethylene-polphenyl isocyanate-mixture (8: 1) is mixed.By the mixture 1.2 parts polyvinyl alcohol, Emulsification is carried out in the mixture of 0.05 part of antifoaming agent and 51.6 parts of water until reaching desirable particle size.To this breast 2.8 part of 1,6- hexanediamine mixture of the addition in 5.3 parts of water in liquid.By mixture stirring until polymerisation is complete At.
The capsule suspension liquid of acquisition is stablized by adding 0.25 part of thickener and 3 parts of dispersant.It is described Capsule suspension liquid preparation includes 28% active constituent.The diameter of the medium capsule is 8 microns -15 microns.
It is administered to gained preparation as the aqueous suspension suitable for this destination device on seed.
Abbreviation inventory：
AIBN=azodiisobutyronitrile
DMF=dimethylformamide
Bis--diisopropylethylamine of DIPEA=N, N-
EtOAc=ethyl acetate
HCl=hydrochloric acid
Mp=fusing point
DEG C=degree Celsius
MeOH=methanol
NaOH=sodium hydroxide
NBS=N-bromosuccinimide
Min=minute
RT=room temperature
H=hour
TFAA=trifluoroacetic anhydride
THF=tetrahydrofuran
tR=retention time (in minutes)
LC/MS=liquid chromatography-mass spectrography (description of the device and method for LC/MS analyses is given above).
Example 1：This example illustrates 3- [4- (imidazoles -1- ylmethyls) phenyl] -5- (trifluoromethyl) -1,2,4- Evil bis- The preparation of azoles (compound 1.18 of table T1)
Step 1：The preparation of N '-hydroxy-4-methyls-benzenecarboximidamide
It is outstanding to stirring of the 4- methyl benzonitriles (35g, 0.29mol) in ethyl alcohol (220mL) and water (440mL) at RT Added in supernatant liquid hydroxylamine hydrochloride (41.1g, 0.58mol), potassium carbonate (65.4g, 0.47mol) and 8-hydroxyquinoline (0.22g, 1.5mmol).Reaction mixture is heated 4 hours at 80 DEG C.Mixture is cooled to room temperature, 2N HCl is used in combination to be diluted to pH 8.Ethanol evaporation under reduced pressure.Mixture is filtered, be washed with water and is dried under vacuum, to provide title compound. Retention time=0.23 minute LC/MS (method A), 151.0 (M+H).
Step 2：3- (p-methylphenyl) -5- (trifluoromethyl) -1, the preparation of 2,4- oxadiazoles
In 0 DEG C of N '-hydroxy-4-methyls-benzenecarboximidamide (38.7g, 0.25mol) to stirring in 2- methyltetrahydrofurans TFAA is added in solution in (750mL).Reaction mixture is stirred two hours at 15 DEG C, is then diluted with water.By organic layer Sodium bicarbonate solution, ammonium chloride solution, water washing are used in separation successively, dried over sodium sulfate, filtering, and are evaporated to drying.It will be thick Product carries out flash chromatography on silica gel (750g prepacked columns) with heptane/EtOAc (99: 1 to 90: 10), to provide in clarification The title compound of grease, cures after storage.
Retention time=1.15 minute LC/MS (method A), do not detect quality.
1H NMR (400MHz, CDCl3)δppm：8.00 (d, 2H), 7.32 (d, 2H), 2.45 (s, 3H).
19F NMR (400MHz, CDCl3)δppm：-65.41(s).
Step 3a：3- [4- (bromomethyl) phenyl] -5- (trifluoromethyl) -1, the preparation of 2,4- oxadiazoles
Under argon gas by 3- (p-methylphenyl) -5- (trifluoromethyl) -1 in tetrachloromethane (480mL), 2,4- oxadiazoles The stirring mixture of (56.0g, 0.24mol) and NBS (45.4g, 0.25mol) are heated to 70 DEG C.Addition AIBN (4.03g, 24mmol), and by reaction mixture it is stirred 18 hours at 65 DEG C.Mixture is cooled to room temperature, and uses dichloromethane It is diluted with water, and detaches each layer.Organic layer is washed with sodium bicarbonate solution, it is dried over sodium sulfate, it filters and is evaporated to dryness It is dry.Thick residue is subjected to flash chromatography on silica gel (750g prepacked columns) with hexamethylene/EtOAc 100: 0 to 95: 5, with The title compound of white solid, mp are provided：58℃-63℃.
1H NMR (400MHz, CDCl3)δppm：8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).
19F NMR (400MHz, CDCl3)δppm：-65.32(s).
3- [4- (two bromomethyls) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles are separated into the pair of white solid Product, mp：61℃-66℃.
1H NMR (400MHz, CDCl3)δppm：8.15 (d, 2H), 7.73 (d, 2H), 6.68 (s, 1H).
19F NMR (400MHz, CDCl3)δppm：-65.34(s).
Step 3b：From 3- [4- (two bromomethyls) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles prepare 3- [4- (bromine first Base) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles
At 5 DEG C, to the 3- of the stirring in acetonitrile (95mL), water (1.9mL) and DIPEA (6.20ml, 35.7mmol) [4- (bromomethyl) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles and 3- [4- (two bromomethyls) phenyl] -5- (fluoroforms Base) -1, addition diethyl phosphite (4.7mL, 35.7mmol) in 2,4- oxadiazoles (10.2g), 1: 9 scalemic thereof.It will mixing Object stirs two hours at 5 DEG C -10 DEG C, adds water and 1M HCl, and acetonitrile is evaporated under reduced pressure.By white slurries with two Chloromethanes extracts three times.Combined organic layer is dried over sodium sulfate, and filter.Solvent is removed under reduced pressure, and is made Gained thick residue carries out flash chromatography on silica gel (40g prepacked columns) with hexamethylene/EtOAc 99: 1 to 9: 1, to provide 3- [4- (bromomethyl) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles.
1H NMR (400MHz, CDCl3)δppm：8.11 (d, 2H), 7.55 (d, 2H), 4.53 (s, 2H).
19F NMR (400MHz, CDCl3)δppm：-65.32(s).
Step 4：3- [4- (imidazoles -1- ylmethyls) phenyl] -5- (trifluoromethyl) -1, the preparation of 2,4- oxadiazoles
By 3- [4- (bromomethyl) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles (100mg, 0.31mmol), imidazoles The solution of (1.5 equivalents, 0.46mmol) and potassium carbonate (2 equivalents, 0.62mmol) in acetonitrile (3.0mL) in micro-wave oven It is heated 30 minutes at 120 DEG C.It is removed by filtration solid and is washed with ethyl acetate, and evaporate mother liquor to provide thick remnants Object.Other solvent is removed under reduced pressure, and by gained residue in silica gel (hexamethylene: EtOAc eluents gradient 1: 0 To 0: 1) by purification by flash chromatography on, to obtain 3- [4- (imidazoles -1- ylmethyls) phenyl] -5- (three in yellow solid Methyl fluoride) -1,2,4- oxadiazoles.Retention time=0.69 minute LC/MS (method A), 295 (M+H).mp：45℃-55℃
1H NMR (400MHz, CDCl3)δppm：8.22 (d, 2H), 7.61 (d, 2H), 7.28 (d, 2H), 7.14 (s, 1H), 5.20 (s, 2H).
19F NMR (400MHz, CDCl3)δppm：-65.39(s).
Example 2：This example illustrates 3- [4- [(4- cyclopenta triazol-1-yl) methyl] phenyl] -5- (trifluoromethyl) - The preparation of 1,2,4- oxadiazole (compound 1.24 of table T1)
By 3- [4- (bromomethyl) phenyl] -5- (trifluoromethyl) -1, the solution of 2,4- oxadiazoles (153mg, 0.49mmol) It is dissolved in dimethylformamide (1.5mL), isopropanol (1mL) and water (1mL).Nitrine is introduced into gained white suspension Change sodium (64mg), copper sulphate (II) (28mg) and copper cyanider (18mg).Acetylene basic ring penta is introduced into clarification beige coloured suspension Alkane (0.06mL) and triethylamine (1mL), and be at room temperature stirred overnight the light green color turbid solution.It pours the mixture into In separatory funnel containing water and EtOAc, each layer is detached, and aqueous fraction is then extracted with ethyl acetate.By having for merging Machine object is dried over sodium sulfate and is concentrated under reduced pressure, to provide the crude product in green oil.By crude product in silica gel (heptane: EtOAc Eluent gradient 99: 1 to 1: 1) combiflash chromatographies are carried out on, to provide 3- [4- [(the 4- cyclopenta of white solid-like Triazol-1-yl) methyl] phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles.Retention time=1.10 point LC/MS (method A) Clock, 364 (M+H).mp：117℃-119℃
1H NMR (400MHz, CDCl3)δppm：8.12 (d, 2H), 7.39 (d, 2H), 7.22 (s, 1H), 5.57 (s, 1H), 3.18 (m, 1H), 2.09 (m, 2H), 1.75 (m, 2H), 1.70 (m, 4H).
19F NMR (400MHz, CDCl3)δppm：-65.39(s).
Example 3：This example illustrates 3- [4- [1- (6- methoxyl group -3- pyridyl groups) ethyl] phenyl] -5- (fluoroforms Base) -1, the preparation of 2,4- oxadiazoles (compound 1.42 of following table T1)
Step 1：The preparation of 4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] chlorobenzoyl chloride
4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzoic acid (4.00g, 15.0mmol) is suspended in dichloro In methane (90mL), DMF (0.01mL, 0.150mmol) is added, then adds oxalyl chloride (1.46mL, 16.5mmol).It will mixing Object heats 2 hours under reflux.Mixture is evaporated under reduced pressure, to provide the 4- [5- (fluoroforms that 4.15g is in yellow solid Base) -1,2,4- oxadiazole -3- bases] chlorobenzoyl chloride.
Step 2：The system of N- methoxy-. N-methyls -4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzamide It is standby
At room temperature by 4- [5- (trifluoromethyl) -1,2, the 4- oxadiazoles-from step 1 in dichloromethane (20mL) 3- yls] solution of chlorobenzoyl chloride (4.15g, 14.6mmol) is added dropwise to the N- methoxyl group methylamines in dichloromethane (80mL) In the agitating solution of (1.10g, 17.5mmol) and triethylamine (3.10ml, 21.8mmol).Mixture is stirred at room temperature 18 Hour.Reaction mixture is poured into water, is extracted twice with dichloromethane.Combined organic layer is washed with brine, through sulfuric acid Sodium is dried, and is filtered.Solvent is removed under reduced pressure, and by gained thick residue in silica gel (heptane: EtOAc eluents Gradient 9: 1 to 65: 35) carrying out flash chromatography on, to provide the N- methoxy-. N-methyls -4- [5- (fluoroforms that 4.12g is in solid Base) -1,2,4- oxadiazole -3- bases] benzamide.Retention time=0.97 minute LC/MS (method A), 302 (M+H).
1H NMR (400MHz, CDCl3)δppm：8.18 (d, 2H), 7.84 (d, 2H), 3.56 (s, 3H), 3.40 (s, 3H).
Step 3：The preparation of 4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzaldehyde
It, will be in toluene under argon gas at -78 DEG C in the 75-mL multinecked flasks equipped with blender, thermometer DIBAL-H 1.0M (16mL, 16.0mmol) are added dropwise to the N- methoxy-. N-methyls-in 2- methyltetrahydrofurans (90mL) In the solution of 4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzamide (4.10g, 13.3mmol).By mixture It stirs 2 hours at -78 DEG C, and elevates the temperature to 0 DEG C in one hour.Complete conversion is observed by LC-MS.It will mix Object is closed to be quenched by the way that saturated ammonium chloride solution is added dropwise.The precipitation of white solid has occurred.4M HCl are added until completely molten Solution.Mixture is extracted with ethyl acetate three times.Combined organic matter is dried over magnesium sulfate and evaporated, to provide in cream-coloured solid The crude product of body.Crude product is subjected to combiflash chromatographies on silica gel (heptane: EtOAc eluents gradient 99: 1 to 90: 10), with 4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzaldehyde of the white solids of 2.93g is provided.mp：40℃-50℃.
1H NMR (400MHz, CDCl3)δppm：10.12 (s, 1H), 8.31 (d, 2H), 8.05 (d, 2H).
19F NMR (400MHz, CDCl3)δppm：-65.29(s).
Step 4：The preparation of 1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] phenyl] ethyl alcohol
In dry 50mL flasks and under argon gas, by 4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzaldehyde (1.36mol) is dissolved in THF (10mL) and is cooled to -78 DEG C by dry ice acetone bath.Methyl is introduced dropwise into this solution Magnesium bromide (0.70mL, 2.03M, in ether).Mixture is stirred 1 hour at -78 DEG C, and then uses saturated ammonium chloride Aqueous solution is quenched.The dry ice bath is removed, and reaction is stirred at room temperature 5 minutes.Then it is extracted with ethyl acetate.It will merge Organic matter it is dried over sodium sulfate and be concentrated under reduced pressure, to provide the crude product in colorless oil.By crude product in silica gel (heptane： EtOAc eluents gradient 99: 1 to 1: 1) combiflash chromatographies are carried out on, to provide the 1- [4- [5- (three of white solid-like Methyl fluoride) -1,2,4- oxadiazole -3- bases] phenyl] ethyl alcohol.
1H NMR (400MHz, CDCl3)δppm：8.12 (d, 2H), 7.54 (d, 2H), 5.00 (s, 1H), 1.54 (d, 3H).
19F NMR (400MHz, CDCl3)δppm：-65.31(s).
Step 5：The preparation of 1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] phenyl] ethyl ketone
In dry 50mL flasks and under argon gas, by 1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzene Base] ethyl alcohol (1.36mol) is dissolved in dichloromethane (10mL).Manganese oxide (40.6mmol) is introduced into this solution, and should Heterogeneous mixture is stirred at room temperature overnight.Then reaction solution is filtered through Celite pad, and is washed with dichloromethane Afterwards, combined organic matter is concentrated under reduced pressure, with provide white solid-like crude product 1- [4- [and 5- (trifluoromethyl) -1,2, 4- oxadiazole -3- bases] phenyl] ethyl ketone, it is directly used without further purification.
1H NMR (400MHz, CDCl3)δppm：8.24 (d, 2H), 8.12 (d, 2H), 2.67 (s, 1H), 1.56 (d, 3H).
19F NMR (400MHz, CDCl3)δppm：-65.39(s).
Step 6：4- methyl-N- [(E) -1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] phenyl] ethylidene Amino] benzsulfamide preparation
In dry 50mL flasks and under argon gas, by 1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] benzene Base] ethyl ketone (1.05mol) is dissolved in methanol (10mL).4- Methyl benzenesulfonyls hydrazine (1.16mmol) is introduced into this solution, and And gained white suspension is stirred at room temperature overnight.Then reaction solution is concentrated under reduced pressure, it is white solid to provide The crude product 4- methyl-N- [(E) -1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] phenyl] ethyleneimino] of body shape Benzsulfamide directly uses it without further purification.
1H NMR (400MHz, CDCl3)δppm：8.12 (d, 2H), 7.93 (d, 2H), 7.81 (d, 2H), 7.60 (sbr, 1H), 7.36 (d, 2H), 2.44 (s, 3H), 2.17 (s, 3H).
19F NMR (400MHz, CDCl3)δppm：-65.34(s).
Step 7：3- [4- [1- (6- methoxyl group -3- pyridyl groups) ethyl] phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles Preparation
In dry 10mL flasks and under argon gas, by 4- methyl-N- [(E) -1- [4- [5- (trifluoromethyl) -1,2,4- Oxadiazole -3- bases] phenyl] ethyleneimino] benzsulfamide (0.47mol) is dissolved in dioxane (1.4mL).Into this solution 2- methoxypyridines boric acid (0.71mmol) is introduced, and gained beige coloured suspension is stirred 3 hours at 110 DEG C.It is cooled to After room temperature, then reaction solution is concentrated under reduced pressure and crude product is carried out on silica gel combiflash chromatographies (hexamethylene: EtOAc eluents gradient 99: 1 to 4: 1), to provide the 3- [4- [1- (6- methoxyl group -3- pyridyl groups) ethyl] in yellow oily Phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles.
1H NMR (400MHz, CDCl3)δppm：8.07 (d, 1H), 8.03 (d, 2H), 7.38 (d, 1H), 7.36 (d, 2H), 6.69 (d, 1H), 4.18 (q, 1H), 3.92 (s, 3H), 1.67 (d, 3H).
19F NMR (400MHz, CDCl3)δppm：-65.38(s).
Example 4：This example illustrates 3- [4- [1- (3,5- dimethyl pyrazole -1- bases) ethyl] phenyl] -5- (fluoroforms Base) -1, the preparation of 2,4- oxadiazoles (compound 1.303 of following table T1)
Step 1：3- [4- (1- bromoethyls) phenyl] -5- (trifluoromethyl) -1, the preparation of 2,4- oxadiazoles
Through 30 minutes to 1- [4- [5- (trifluoromethyl) -1,2,4- oxadiazole -3- bases] phenyl] ethyl alcohol (1.15g, 4.45mmol) being cooled to using ice bath in 0 DEG C of solution in dichloromethane (15mL) add tribromo phosphine (0.465ml, 4.90mmol) and by reaction mixture stir 1.5 hours.Then, be cooled with an ice bath content, and introduces 10% sodium pyrosulfite (50ml).After 15 minutes, water layer is extracted with dichloromethane, and total organic layer of merging is washed with water, and through Na2SO4 It is dry, it filters and is concentrated under reduced pressure.Gained thick residue (is used into hexamethylene by the combiflash chromatographies on silica gel Alkane is as eluent) it is purified, to provide pure 3- [4- (1- bromoethyls) phenyl] -5- (fluoroforms of white solid-like Base) -1,2,4- oxadiazoles (1g, 71% yield).
1H NMR (400MHz, DMSO-d6) δ ppm：8.07 (m, 2H), 7.75 (m, 2H), 5.76 (s, 1H), 5.59 (q, 1H), 2.02 (d, 3H).
Step 2：3- [4- [1- (3,5- dimethyl pyrazole -1- bases) ethyl] phenyl] -5- (trifluoromethyl) -1,2,4- Evil bis- The preparation of azoles.
By 3- [4- (1- bromoethyls) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles (150mg, 0.47mmol), 3,5- Dimethyl pyrazole (0.07g, 0.70mmol) and potassium carbonate (0.130g, 0.93mmol) are dissolved in the acetonitrile (5mL) in microwave bottle In.Then the mixture is heated 30 minutes in microwave at 100 DEG C.The reaction mixture is carried out with water (20mL) dilute It releases, and is extracted with ethyl acetate.By the organic layer aqueous salt solu-tion of total merging, through anhydrous Na2SO4It is dry, mistake It filters and is concentrated under reduced pressure.Gained thick residue is passed through into the combiflash chromatographies (hexamethylene: EtOAc is eluted on silica gel Liquid gradient 92: 8) being purified, and glues block-like pure 3- [4- [1- (3,5- dimethyl pyrazole -1- bases) in yellowish glue to provide Ethyl] phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles (55mg, 35%).Retention time=1.61 point LC/MS (method C) Clock, 337 (M+H).
1H NMR (400MHz, CDCl3)δppm：8.04 (d, 2H), 7.25 (m, 2H), 5.87 (s, 1H), 5.41 (q, 1H), 2.30 (s, 3H), 2.12 (s, 3H), 1.95 (d, 3H).
Example 5：This example illustrates 3- [4- [2- (3,5- dimethyl pyrazole -1- bases) ethyl] phenyl] -5- (fluoroforms Base) -1, the preparation of 2,4- oxadiazoles (compound 1.309 of following table T1)
Step 1：3- [4- (2- bromoethyls) phenyl] -5- (, trifluoromethyl) and -1, the preparation of 2,4- oxadiazoles
Hydrochloric acid hydroxylamine is added into solution of 4- (2- bromoethyls) benzonitriles (2.0g, 9.5mmol) in ethyl alcohol (32mL) (2 equivalents, 19mmol) then adds triethylamine (4.5 equivalents, 43mmol).Reaction content is stirred 12 at ambient temperature Hour, and volatile matter is then removed under reduced pressure.Obtained thick material is dissolved in tetrahydrofuran (60mL), ice bath is used Be cooled to 0 DEG C, and slowly introduce trifluoroacetic anhydride (3 equivalents, 29mmol) at 0 DEG C, be then added dropwise pyridine (4 equivalents, 38mmol).After being warming up to 25 DEG C and stirring 5 hours, reaction mixture water (100mL) is diluted and is extracted with ethyl acetate. By total organic layer 1N HCl and the aqueous salt solu-tion of merging.By the organic layer therefore obtained through anhydrous Na2SO4It is dried, It filters and is concentrated under reduced pressure.Gained thick residue (is used into 30% second in hexane by the flash chromatography on silica gel Acetoacetic ester is as eluent) it is purified, it is in block-like pure 3- [4- (2- bromoethyls) the phenyl] -5- of colourless gluing to provide (trifluoromethyl) -1,2,4- oxadiazoles (1.75g, 57% yield).
1H NMR (400MHz, CDCl3)δppm：8.09 (d, 2H), 7.39 (d, 2H), 3.62 (t, 2H), 3.26 (t, 2H)
Step 2：3- [4- [2- (3,5- dimethyl pyrazole -1- bases) ethyl] phenyl] -5- (trifluoromethyl) -1,2,4- Evil bis- The preparation of azoles.
By 3- [4- (2- bromoethyls) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles (0.150g, 0.467mmol), 3, 5- dimethyl -1H- pyrazoles (1.5 equivalents, 0.701mmol) and potassium carbonate (0.30g, 0.934mmol) are dissolved in microwave bottle Acetonitrile (5mL) in, and by mixture in the presence of microwave radiation at 100 DEG C heat 30min.Then the reaction is mixed It closes object to be diluted with water (20mL), and is extracted with ethyl acetate.By the total organic layer water and saline solution of merging Washing.By the organic layer therefore obtained through anhydrous Na2SO4It is dried, filters and is concentrated under reduced pressure.Gained is slightly remaining Object is purified by the flash chromatography (30% ethyl acetate in hexane is used to be used as eluent) on silica gel, is in provide Colourless block-like pure 3- [4- [2- (3,5- dimethyl pyrazole -1- bases) ethyl] phenyl] -5- (trifluoromethyl) -1,2,4- of gluing Oxadiazole (0.03g, 16% yield).Retention time=1.67 minute LC/MS (method C), 337 (M+H).
1H NMR (400MHz, CDCl3)δppm：8.03 (m, 2H), 7.19 (m, 2H), 5.73 (s, 1H), 4.21 (t, 2H), 3.21 (t, 2H), 2.28 (s, 3H), 1.88 (s, 3H).
Example 6：This example illustrates 1- [2- [4- [5- (trifluoromethyl) -1,2,4- oxadiazoles-yl] phenyl] ethyl] The preparation of pyrazoles -4- Ethyl formates (compound 1.310 of lower Table A)
By 3- [4- (2- bromoethyls) phenyl] -5- (trifluoromethyl) -1,2,4- oxadiazoles (0.150g, 0.467mmol) with And 1H- pyrazoles -4- Ethyl formates (0.03g, 0.08mmol) are suspended in acetonitrile (1mL), and introduce potassium carbonate (0.30g, 0.934mmol), it and stirs the mixture for 16 hours.Then the reaction mixture is diluted with water (20mL), and used Ethyl acetate is extracted.By the total organic layer water and aqueous salt solu-tion of merging.By the organic layer therefore obtained through anhydrous Na2SO4It is dried, filters and is concentrated under reduced pressure.Gained thick residue (is used by the flash chromatography on silica gel 30% ethyl acetate in hexane is as eluent) it is purified, to provide the pure 1- [2- [4- [5- of white solid-like (trifluoromethyl) -1,2,4- oxadiazole -3- bases] phenyl] ethyl] pyrazoles -4- Ethyl formates (0.03g, 20% yield).MP：108 ℃-110℃.Retention time=1.57 minute LC/MS (method C), 381 (M+H).
1H NMR (400MHz, CDCl3)δppm：8.05 (m, 2H), 7.96 (s, 1H), 7.69 (s, 1H), 7.23 (m, 2H), 4.41 (t, 2H), 4.28 (q, 2H) 3.30 (t, 2H), 1.33 (m, 3H).
Using structural unit appropriate (compound with formula (II) and (III)), carry out in a joint manner following general Program is to provide the compound with formula (I).The compound prepared by following assembled scheme is analyzed using LC/MS methods B.
By illustrating, by 3- [4- (2-bromomethylphenyl] -5- (trifluoromethyl) -1, (0.03mmol is in 1000 for 2,4- oxadiazoles In μ L acetonitriles) it is transferred in the microwave bottle containing amine derivative (0.03mmol), potassium carbonate (0.06mmol) with formula (II), And it is stirred 20 minutes at 120 DEG C under microwave radiation in parallel microwave device.Solvent is removed under nitrogen flowing.By gained Thick residue is dissolved in the mixture of MeOH (250 μ L) and DMA (500 μ L), and directly presents that be used to prepare type LC/MS pure Change, the compound with formula (I) is provided.The structure of isomers is specified by NMR technology.
Table T1：The fusing point (mp) and/or LC/MS data (retention time (t of compound with formula (I)R))：
74IIC181950
Biological example
The general example of leaf disk test in the orifice plate：
The leaf disk or leaf section of different plant species are cut from the plant being grown in greenhouse.By the leaf disk of cutting or Leaf section is placed on the water agar in porous plate (24 hole specification).Before inoculation (preventative) or later (therapeutic), leaf is justified Piece test solution spraying.Compound to be tested is prepared into DMSO solution (maximum 10mg/ml), it will sprayed it It is preceding to be diluted to debita spissitudo with 0.025%Tween20.It is (temperature, relatively wet in the condition of restriction according to corresponding test system Degree, light etc.) under be incubated the leaf disk or leaf section of inoculation.Depending on disease system, after being inoculated with 3 to 14 days, disease levels are carried out Single assessment.Then the disease control percentage relative to untreated inspection leaf disk or leaf section is calculated.
The general example of Liquid Culture test in the orifice plate：
The mycelium segment of fungi or conidium is (fresh from the liquid culture of the fungi or from low-temperature storage object Prepare) it is directly mixed in nutrient broth.The DMSO solution for testing compound (maximum 10mg/ml) is used by the factor 50 0.025% Tween20 is diluted, and this solution of 10 μ l is pipetted microtiter plate (96 hole gauges with pipette Lattice) in.Then the nutrient broth comprising the fungal spore/mycelium segment is added to wherein, to provide test compound Final concentration.By test board in 24 DEG C and the black undercover incubation of 96% relative humidity.Depending on disease system, 2 to 7 days it The inhibition of fungi growth is measured by photometry afterwards, and calculates the antifungal activity hundred for untreated inspection object Divide ratio.
Example 1：For Fungicidally active/wheat/leaf disk preventive treatment (leaf rust) of Puccinia recondita f. sp. tritici
Wheat leaf section cultivar Kanzler is placed on the agar of porous plate (24 hole specification), and with being diluted in water In preparation test compound spray.1 day after application, these leaf disks are inoculated with the spore suspension of fungi.In climatic chamber In, it was illuminated under/12 hours dark light schemes at 12 hours, the leaf through inoculation is incubated under 19 DEG C and 75% relative humidity (rh) Section, and compound activity is assessed as, when the disease for occurring proper level in untreated inspection leaf section is damaged (after application 7 to 9 days), the disease control percentage compared with untreated.
In this test, leaf disk phase is compareed with extensive the untreated of disease development is shown when under the same conditions Than when, following compound provides at least 80% disease control at 200ppm in the preparation of application.
Compound (come from table T1) 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,1.10,1.11,1.12, 1.15、1.16、1.18、1.19、1.21、1.22、1.23、1.24、1.25、1.26、1.27、1.28、1.29、1.30、1.32、 1.33、1.34、1.35、1.36、1.37、1.39、1.40、1.41、1.42、1.43、1.44、1.45、1.46、1.47、1.48、 1.49、1.50、1.52、1.53、1.55、1.56、1.57、1.58、1.60、1.61、1.62、1.63、1.65、1.67、1.73、 1.74、1.75、1.76、1.79、1.80、1.81、1.82、1.83、1.85、1.86、1.87、1.88、1.89、1.90、1.91、 1.93、1.94、1.95、1.96、1.99、1.101、1.102、1.105、1.107、1.108、1.109、1.112、1.118、 1.119、1.120、1.121、1.122、1.123、1.124、1.125、1.126、1.128、1.129、1.131、1.132、 1.133、1.135、1.136、1.137、1.139、1.141、1.144、1.145、1.146、1.147、1.148、1.149、 1.150、1.151、1.154、1.156、1.157、1.158、1.171、1.174、1.186、1.192、1.193、1.200、 1.203、1.204、1.206、1.207、1.208、1.209、1.212、1.213、1.214、1.215、1.219、1.222、 1.224、1.226、1.229、1.232、1.233、1.236、1.237、1.238、1.239、1.240、1.243、1.244、 1.245、1.246、1.247、1.248、1.249、1.250、1.251、1.252、1.253、1.254、1.255、1.256、 1.259、1.260、1.261、1.262、1.263、1.265、1.266、1.267、1.268、1.269、1.270、1.271、 1.273、1.274、1.275、1.276、1.277、1.278、1.279、1.280、1.281、1.282、1.283、1.285、 1.286、1.287、1.288、1.289、1.290、1.292、1.294、1.295、1.296、1.297、1.298、1.299、 1.301,1.302,1.303,1.304,1.305,1.306,1.308,1.310 and 1.312.
Example 2：For Fungicidally active/wheat/leaf disk cure (leaf rust) of Puccinia recondita f. sp. tritici
Wheat leaf section cultivar Kanzler is placed on the agar in porous plate (24 hole specification).Then fungi is used Spore suspension is inoculated with leaf section.Under 19 DEG C and 75% relative humidity, storage board in the dark.1 day after inoculation, it is applied in water In diluted formulated test compound.In climatic chamber, illuminated under/12 hours dark light schemes at 12 hours, 19 DEG C and 75% relative humidity under be incubated leaf section, and compound activity is assessed as, and is fitted in untreated inspection leaf section When horizontal disease damage (after application 6 to 8 days), the disease control percentage compared with untreated.
In this test, leaf disk phase is compareed with extensive the untreated of disease development is shown when under the same conditions Than when, following compound provides at least 80% disease control at 200ppm in the preparation of application.
Compound (come from table T1) 1.1,1.2,1.3,1.5,1.6,1.8,1.9,1.10,1.11,1.15,1.16,1.18, 1.19、1.22、1.23、1.25、1.26、1.27、1.30、1.32、1.33、1.34、1.35、1.36、1.38、1.39、1.40、 1.41、1.42、1.43、1.44、1.45、1.46、1.49、1.54、1.55、1.56、1.61、1.62、1.67、1.71、1.76、 1.77、1.78、1.79、1.80、1.81、1.82、1.83、1.85、1.86、1.87、1.88、1.89、1.90、1.91、1.93、 1.96、1.97、1.99、1.101、1.102、1.118、1.119、1.120、1.121、1.123、1.124、1.128、1.129、 1.131、1.132、1.133、1.134、1.135、1.136、1.137、1.141、1.143、1.144、1.145、1.146、 1.147、1.148、1.149、1.150、1.151、1.154、1.156、1.174、1.192、1.200、1.203、1.206、 1.207、1.208、1.209、1.213、1.214、1.215、1.219、1.222、1.226、1.229、1.232、1.233、 1.236、1.237、1.238、1.239、1.243、1.244、1.245、1.246、1.247、1.248、1.253、1.254、 1.255、1.256、1.258、1.259、1.260、1.261、1.263、1.264、1.265、1.266、1.267、1.268、 1.269、1.270、1.271、1.272、1.273、1.274、1.275、1.277、1.279、1.280、1.281、1.283、 1.285、1.287、1.288、1.290、1.291、1.292、1.293、1.294、1.295、1.296、1.297、1.298、 1.299,1.3021.303,1.304,1.305,1.306 and 1.312.
Example 3：For Fungicidally active/soybean/leaf disk preventive treatment (Asian Soybean Rust) of Phakopsora pachyrhizi
Soybean leaf disk is placed on the water agar in porous plate (24 hole specification), and with the preparation being diluted in water Test compound is sprayed.Using one day after, by being inoculated with leaf disk in inferior leads surface spray spore suspension.In gas It waits in room, it, will with 12h illuminations/day and 75%rh in the dark after the incubation period of the 24-36 hours under 20 DEG C and 75%rh Leaf disk is maintained at 20 DEG C.When it is untreated inspection leaf disk in occur proper level disease damage when (after application 12 to 14 days), it is the disease control percentage compared with untreated by the Activity Assessment of compound.
In this test, leaf disk phase is compareed with extensive the untreated of disease development is shown when under the same conditions Than when, following compound provides at least 80% disease control at 200ppm in the preparation of application.
Compound (come from table T1) 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.9,1.10,1.11,1.15,1.16, 1.17、1.18、1.19、1.20、1.21、1.22、1.23、1.24、1.25、1.26、1.27、1.28、1.30、1.32、1.33、 1.34、1.35、1.36、1.39、1.40、1.41、1.42、1.43、1.49、1.56、1.59、1.61、1.79、1.85、1.86、 1.87、1.88、1.90、1.91、1.93、1.96、1.99、1.101、1.102、1.129、1.136、1.146、1.147、1.148、 1.149、1.150、1.151、1.152、1.153、1.154、1.156、1.157、1.158、1.171、1.174、1.177、 1.184、1.185、1.186、1.187、1.190、1.192、1.193、1.194、1.195、1.198、1.200、1.201、 1.203、1.204、1.205、1.206、1.207、1.208、1.209、1.212、1.213、1.214、1.215、1.219、 1.222、1.223、1.224、1.226、1.227、1.228、1.229、1.230、1.232、1.233、1.236、1.237、 1.238、1.239、1.240、1.243、1.244、1.245、1.246、1.247、1.248、1.252、1.253、1.256、 1.259、1.260、1.261、1.263、1.264、1.265、1.266、1.267、1.268、1.270、1.273、1.274、 1.275、1.276、1.277、1.278、1.279、1.280、1.283、1.285、1.286、1.288、1.290、1.303、 1.304,1.305,1.306,1.310 and 1.312.
Example 4：For Fungicidally active/cucumber/preventive treatment (charcoal of melon small cluster shell (melon thorn disk spore) liquid culture Subcutaneous ulcer disease)
Fungus conidium from low-temperature storage is directly mixed in nutrient broth (PDB- potato dextrose broths). After (DMSO) solution that will test compound is placed in microtiter plate (96 hole specification), the battalion containing fungal spore is added Support meat soup.Test board is incubated at 24 DEG C and the inhibition by photometric measurement to growth in 3 to 4 days after application.
In this test, when under the same conditions compared with the untreated control for showing the development of extensive disease, Following compound provides at least 80% disease control at 20ppm in the preparation of application.
Compound (come from table T1) 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,1.10,1.15,1.16, 1.17、1.18、1.19、1.20、1.21、1.22、1.23、1.24、1.25、1.26、1.27、1.28、1.29、1.30、1.32、 1.33、1.34、1.35、1.36、1.37、1.38、1.39、1.40、1.41、1.42、1.43、1.44、1.45、1.46、1.47、 1.48、1.49、1.50、1.51、1.52、1.54、1.55、1.56、1.57、1.58、1.59、1.60、1.61、1.62、1.63、 1.64、1.65、1.66、1.67、1.68、1.69、1.70、1.72、1.73、1.74、1.75、1.76、1.77、1.79、1.80、 1.81、1.82、1.83、1.84、1.85、1.86、1.87、1.88、1.89、1.90、1.91、1.92、1.93、1.94、1.95、 1.96、1.97、1.98、1.99、1.100、1.101、1.102、1.103、1.104、1.106、1.107、1.108、1.109、 1.110、1.111、1.112、1.113、1.114、1.115、1.116、1.117、1.118、1.119、1.120、1.121、 1.122、1.124、1.126、1.127、1.128、1.129、1.130、1.131、1.132、1.133、1.135、1.136、 1.137、1.138、1.140、1.142、1.143、1.144、1.146、1.147、1.148、1.149、1.150、1.151、 1.152、1.154、1.157、1.158、1.171、1.174、1.184、1.185、1.186、1.188、1.189、1.190、 1.191、1.192、1.193、1.194、1.198、1.200、1.203、1.204、1.205、1.206、1.207、1.208、 1.209、1.212、1.213、1.214、1.215、1.219、1.222、1.223、1.224、1.226、1.227、1.228、 1.229、1.232、1.233、1.236、1.237、1.238、1.239、1.240、1.243、1.244、1.245、1.246、 1.247、1.248、1.249、1.250、1.251、1.252、1.253、1.254、1.255、1.256、1.257、1.258、 1.259、1.260、1.261、1.262、1.263、1.264、1.265、1.266、1.267、1.268、1.269、1.270、 1.273、1.274、1.275、1.276、1.277、1.278、1.279、1.280、1.281、1.283、1.284、1.285、 1.286、1.287、1.288、1.289、1.290、1.292、1.294、1.295、1.296、1.297、1.298、1.299、 1.302,1.303,1.304,1.305,1.306,1.307,1.309 and 1.312.
Example 5：For Fungicidally active/broad bean/leaf disk preventive treatment (rust of broad bean) of broad bean uromyce
Broad bean leaf disk is placed on the water agar in porous plate (96 hole specification), and diluted 10 μ l will be matched in acetone The test compound and spreading agent of system are pipetted with pipette on leaf disk.Two hours after, by being sprayed in lower part leaf surface Mist spore suspension is inoculated with leaf disk.By leaf disk at 22 DEG C, with 18 hours days and 70% relative humidity in climatic chamber It is incubated.When occurring the disease damage of proper level in untreated inspection leaf disk (after application 12 days), by compound Activity Assessment is the disease control percentage compared with untreated.
In this test, leaf disk phase is compareed with extensive the untreated of disease development is shown when under the same conditions Than when, following compound provides at least 80% disease control at 100ppm in the preparation of application.
Compound (come from table T1) 1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,1.10,1.11,1.12, 1.13,1.14,1.15,1.16,1.17,1.18,1.19 and 1.20.

Claims (15)

1. one kind having the compound of formula (I)：
Wherein
N is 1 or 2；
A1Indicate N or CR1, wherein R1Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethyoxyl or Difluoro-methoxy；
A2Indicate N or CR2, wherein R2Indicate hydrogen, halogen, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxyl group, ethyoxyl or Difluoro-methoxy；
A3Indicate N or CR3, wherein R3Indicate hydrogen or halogen；
A4Indicate N or CR4, wherein R4Indicate hydrogen or halogen；And
Wherein A1、A2、A3And A4In 0 or 1 or 2 be N；
R5And R6Independently selected from hydrogen, C1-4Alkyl, halogen, cyano, trifluoromethyl and difluoromethyl, or
R5And R6Cyclopropyl is formed with together with the carbon atom that they are shared；
Z is selected from Z1、Z2、Z3、Z4、Z5Or Z6；Wherein
Z1It indicates to be keyed to C (R by C-C5)(R6) heterocycle, wherein the heterocyclyl moieties be in loop system contain 1 Nitrogen and 5 yuan or 6 yuan of non-aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, the group It is made of the following terms：O、S、N、NR7, C (O) or S (O)2, condition is that the heterocycle cannot be continuous containing 2 selected from O and S Atom；
Z2It indicates to be keyed to C (R by C-C5)(R6) heteroaryl, wherein the heteroaryl moieties be in loop system contain 1 Nitrogen-atoms and 5 yuan or 6 yuan of aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, should Group is made of the following terms：O, S, N or NR7；
R7It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl amino carbonyl Base, N, bis- C of N-1-4Alkyl amino-carbonyl, C1-4Alkyl sulphonyl, N-C1-2Alkyl amino sulfonyl or N, bis- C of N-1-2Alkyl ammonia Base sulfonyl；And
Wherein for Z1And Z2, the heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 38Can be identical or different Substituent group substitution；
R8It is cyano, halogen, hydroxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alcoxyl Base, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl amino, C1-4Alkyl Carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl or C1-4Alkoxycarbonyl amino；
Z3It indicates to be keyed to C (R by C-N5)(R6) heterocycle, wherein the heterocyclyl moieties be in loop system contain 1 Nitrogen and 5 yuan or 6 yuan of non-aromatic rings for optionally including 1,2 or 3 other ring members independently selected from the following group, the group It is made of the following terms：O、S、N、NR9Or C (=N-O-C1-4Alkyl), condition is that the heterocycle cannot be containing 2 selected from O and S Continuous atom；
Z4It indicates to be keyed to C (R by C-N5)(R6) heteroaryl, wherein the heteroaryl moieties be in loop system containing 1 to 5 yuan of aromatic rings of 4 nitrogen-atoms；
R9It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl amino carbonyl Base or N, bis- C of N-1-4Alkyl amino-carbonyl；And
Wherein for Z3And Z4, the heterocycle or heteroaryl moieties are optionally selected from R by 1,2 or 310Can be identical or different Substituent group substitution；
Wherein R10It indicates：
(i) cyano, halogen, hydroxyl, amino, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Alkoxy C1-4Alkyl, C1-4Halogenated alkoxy, C1-4Alkyl alkylthio base, C1-4Alkyl sulphinyl, C1-4Alkane Base sulfonyl, C1-4Halogenated alkyl sulfanyl, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, bis- C of N-1-4Alkyl ammonia Base, formoxyl, hydroxycarbonyl group, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, amino carbonyl, N-C1-4Alkane Base amino carbonyl, N-C2-4Alkenyl amino carbonyl, N-C2-4Alkynylaminocarbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, N- morpholines are simultaneously Amino carbonyl, N-C1-4Alkoxy amino carbonyl, N-C1-4Alkyl-N-C1-4Alkoxy amino carbonyl, C1-4Alkoxycarbonyl amino, C1-4Alkoxycarbonyl amino C1-4Alkyl, N-C1-4Alkoxy C1-4Alkyl amino-carbonyl, phenyl carbonyloxy group C1-4Alkyl, phenyl carbonyl Base amino C1-4Alkyl, C1-4Alkyl carbonyl oxy, C1-4Halogenated alkyl carbonyloxy group, C1-4Alkyl carbonyl oxy C1-4Alkyl, C1-4Alkyl oxycarbonyl Base amino C1-4Alkyl or (C1-4Alkyl)3Si-；Or
(ii)-C(O)N(Ra)(Rb), wherein：
RaIt is hydrogen, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C1-2Halogen For alkoxy C1-4Alkyl, C3-5Alkenyl, C3-5Alkynyl, amino C1-4Alkyl, N-C1-4Alkyl amino C1-4Alkyl, N, bis- C of N-1-4Alkane Base amino C1-4Alkyl, formoxyl, C1-4Alkyl-carbonyl, C3-4Naphthene base carbonyl, C1-4Halogenated alkyl carbonyl, C1-4Alkyl-carbonyl C1-4 Alkyl, C1-4Alkoxy carbonyl C1-4Alkyl, C1-4Alkyl carbonyl oxy C1-4Alkyl, N-C1-4Alkyl amino-carbonyl C1-4Alkyl, N, N- Two C1-4Alkyl amino-carbonyl C1-4Alkyl, C1-4Alkyl alkylthio base C1-4Alkyl, C1-4Alkyl sulphonyl, C1-4Alkyl sulphonyl C1-4 Alkyl, C1-4Alkyl sulfonyl-amino C1-4Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4Alkane Base, C1-4Alkoxycarbonyl amino C1-4Alkyl or C1-4Haloalkylcarbonylamino C1-4Alkyl, and
RbIt is hydrogen, hydroxyl, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C3-4Alkenyl, C3-4Alkynyl, C3-4Naphthenic base, C3-4Naphthenic base C1-2Alkyl, C1-4Alkoxy, C3-4Alkenyloxy group, C3-4Haloalkenyloxy, Or C3-4Alkynyloxy group；Or
RaAnd RbThe nitrogen-atoms being bonded with them, which forms optionally to contain together, is selected from O, S, S (O)2, C (O) and NRcIn addition Hetero atom or group 4 yuan, 5 yuan or 6 membered rings, wherein RcIt is hydrogen, methyl, methoxyl group, formoxyl or acyl group；Or
(iii)-C(O)O-Rd, wherein：
RdIt is hydrogen, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Cyanoalkyl, hydroxyl C1-4Alkyl, C1-2Alkoxy C1-4Alkyl, C1-2Alkane Oxygroup C1-2Alkoxy C1-4Alkyl, C1-2Halogenated alkoxy C1-4Alkyl, C3-5Alkenyl, C3-4Halogenated alkenyl, C3-4Alkenyloxy group C1-4Alkane Base, C3-5Alkynyl, C3-4Alkynyloxy group C1-4Alkyl, N-C1-3Alkyl amino C1-4Alkyl, N, bis--C of N-1-3Alkyl amino C1-4Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl or C1-4Alkyl-carbonyl-amino C1-4Alkyl；Or
Wherein for Z4, the heteroaryl moieties are optionally by 1 selected from R11Substituent group substitution, and optionally further by 1 Or 2 be selected from R10Can be identical or different substituent group substitution；
Wherein R11It indicates：
(i)C3-8Naphthenic base, C3-8Naphthenic base C1-2Alkyl, N-C3-8Cycloalkyl amino carbonyl, N-C3-8Naphthenic base C1-2Alkyl amino Carbonyl, phenyl, phenyl C1-2Alkyl, phenoxy group C1-2Alkyl, phenyl C1-2Alkyl alkylthio base, heteroaryl moieties therein are to include 1, heteroaryl, the heteroaryl C of 2,3 or 4 heteroatomic 5 yuan or 6 yuan aromatic rings for being individually selected from N, O and S1-2Alkyl, heteroaryl Oxygroup C1-2Alkyl, N- heteroarylaminocarbonyls, heterocyclyl moieties therein are to be individually selected from the miscellaneous of N, O and S comprising 1 or 2 Heterocycle, heterocycle C of 4 yuan of atom to 6 yuan of non-aromatic rings1-6Alkyl, Heterocyclylcarbonyl, benzodioxole base, and And any of the wherein described naphthenic base, phenyl, heteroaryl, heterocycle and benzodioxole base part optionally by 1,2 or 3 are selected from R12Can be identical or different substituent group substitution；Or
(ii)-C(O)N(Re)(Rf), wherein：
ReIt is C3-5Naphthenic base, C3-5Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, heterocyclyl moieties therein be comprising 1,2, Or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition is the heterocycle Heterocycle, the heterocycle C of 2 continuous atoms selected from O and S cannot be contained1-2Alkyl, heteroaryl moieties therein be comprising 1, 2, heteroaryl, the heteroaryl C of 3 or 4 heteroatomic 5 yuan or 6 yuan aromatic rings for being independently chosen from N, O and S1-2Alkyl,
And wherein the naphthenic base, phenyl, heterocycle or heteroaryl moieties optionally by 1 or 2 selected from following item can phase Same or different substituent group substitution：Hydroxyl, amino, formoxyl, acyl group, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, Methoxyl group, ethyoxyl or difluoro-methoxy or the naphthenic base or heterocyclyl moieties are optionally oxo (=O) by 1 or 2 Group replaces, and
RfIt is hydrogen, C1-4Alkyl, C1-4Alkoxy C1-4Halogenated alkyl, C3-4Alkenyl, C3-4Alkynyl, C3-4Naphthenic base or C3-4Naphthenic base C1-2Alkyl；Or
(iii)-C(O)O-Rg, wherein：
RgIt is C3-5Naphthenic base, C3-5Naphthenic base C1-2Alkyl, phenyl, phenyl C1-2Alkyl, heterocyclyl moieties therein be comprising 1,2, Or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition is the heterocycle Heterocycle, the heterocycle C of 2 continuous atoms selected from O and S cannot be contained1-2Alkyl, heteroaryl moieties therein be comprising 1, 2, heteroaryl, the heteroaryl C of 3 or 4 heteroatomic 5 yuan or 6 yuan aromatic rings for being independently chosen from N, O and S1-2Alkyl,
And wherein the naphthenic base, phenyl, heterocycle or heteroaryl moieties optionally by 1 or 2 selected from following item can phase Same or different substituent group substitution：Hydroxyl, formoxyl, acyl group, cyano, halogen, methyl, difluoromethyl, trifluoromethyl, methoxy Base, ethyoxyl or difluoro-methoxy or the naphthenic base or heterocyclyl moieties are optionally by 1 or 2 group for oxo (=O) Substitution；Or
(iv)(C1-4Alkyl)-O-N=C (Rh)-、(C1-4Halogenated alkyl)-O-N=C (Rh)-、(C2-4Alkenyl)-O-N=C (Rh)、 (C2-4Alkynyl)-O-N=C (Rh)-, benzyl-O-N=C (Rh)-, wherein RhIt is hydrogen or methyl；
R12It is cyano, fluorine, chlorine, bromine, methyl, ethyl, formoxyl, methoxyl group, ethyoxyl, difluoromethyl, trifluoromethyl, difluoro first Oxygroup or ethoxy carbonyl；
Z5It indicates to be keyed to C (R by C-N5)(R6) miscellaneous two ring group, wherein the miscellaneous two ring group part is contained in loop system There is 1 nitrogen and optionally includes 7 yuan to 10 yuan saturations, portions of 1,2 or 3 other ring members independently selected from the following group Saturation or partially aromatic fused ring system, the group is divided to be made of the following terms：O、S、N、NR13, C (O) or S (O)2, condition is this Miscellaneous two ring group cannot contain 2 continuous atoms selected from O and S；
Z6It indicates to be keyed to C (R by C-N5)(R6) miscellaneous diaryl, the wherein miscellaneous biaryl moiety is contained in loop system There are 9 yuan of two aromatic systems of 1 to 4 nitrogen-atoms；
R13It is hydrogen, C1-4Alkyl, C1-4Alkoxy, formoxyl, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, N-C1-4Alkyl amino carbonyl Base or N, bis- C of N-1-4Alkyl amino-carbonyl；And
Wherein for Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally selected from R by 1,2,3 or 414Can be identical Or different substituent group substitution；
R14It is cyano, halogen, hydroxyl, formoxyl, C1-4Alkyl, C2-4Alkenyl, C2-4Alkynyl, C1-4Halogenated alkyl, cyano C1-4Alkane Base, C2-4Halogenated alkenyl, C1-4Alkoxy, C1-4Halogenated alkoxy, C3-4Alkenyloxy group, C3-4Alkynyloxy group, N-C1-4Alkyl amino, N, N- Two C1-4Alkyl amino, C1-4Alkyl-carbonyl, C1-4Alkoxy carbonyl, C1-4Alkyl-carbonyl-amino, N-C1-4Alkyl amino-carbonyl, N, Bis- C of N-1-4Alkyl amino-carbonyl or C1-4Alkoxycarbonyl amino, and in addition for Z5, it is oxo (=O)；Or
Wherein for Z5And Z6, miscellaneous two ring group or miscellaneous biaryl moiety are optionally selected from R by 115Substituent group substitution, and Optionally further R is selected from by 1 or 214Can be identical or different substituent group substitution；
R15It is pyridyl group, benzodioxole base oxygroup, phenoxy group or Phenylsulfanyl, wherein phenoxy group and phenyl sulfane Base optionally by selected from chlorine, fluorine, bromine, methyl, ethyl, methoxyl group and ethyoxyl can be identical or different 1,2 or 3 take Replace for base；Or
Its salt or N- oxides.
2. compound according to claim 1, wherein A1It is N or CR1, wherein R1Be hydrogen, chlorine, fluorine, methyl, methoxyl group or Trifluoromethyl, and A2、A3And A4It is C-H.
3. the compound according to claim 1 or claim 2, wherein A1、A2、A3And A4It is C-H.
4. compound according to claim 1, wherein A3It is CR3, and R3It is halogen, and A1、A2And A4It is C-H.
5. compound according to any one of claim 1 to 4, wherein R5And R6It is hydrogen or R5It is hydrogen and R6It is methyl.
6. compound according to any one of claim 1 to 5, wherein Z are Z4。
7. compound according to claim 6, wherein Z4Heteroaryl moieties optionally by 1,2 or 3 be selected from R10Take Replace for base, these substituent groups can be identical or different；
R10It is cyano, halogen, hydroxyl, amino, C1-4Alkyl, C1-4Halogenated alkyl, C1-4Alkoxy, C1-4Alkoxy C1-4Alkyl, C1-4Alkyl alkylthio base, C1-4Halogenated alkyl sulfanyl, N, bis- C of N-1-4Alkyl amino, formoxyl, hydroxycarbonyl group, C1-4Alkyl oxycarbonyl Base, C1-4Alkoxy carbonyl, C3-4Allyloxycarbonyl, C3-4Alkynyloxycar bonyl, amino carbonyl, N-C1-4Alkyl amino-carbonyl, N-C3-4 Alkenyl amino carbonyl, N-C2-4Alkynylaminocarbonyl, N, bis- C of N-1-4Alkyl amino-carbonyl, N- morpholines and amino carbonyl, N-C1-4Alkane Oxygroup amino carbonyl, N-C1-4Alkyl-N-C1-4Alkoxy amino carbonyl, N-C1-4Alkoxy C1-4Alkyl amino-carbonyl, phenyl carbonyl Base amino C1-4Alkyl, C1-4Alkyl carbonyl oxy C1-4Alkyl, C1-4Alkyl-carbonyl-amino C1-4Alkyl, C1-4Alkoxycarbonyl amino C1-4Alkyl or (C1-4Alkyl)3Si-；Or
Z4Optionally R is selected from by 111Substituent group substitution, and optionally further by 1 or 2 be selected from R10Substituent group take Generation；Wherein
R11It is C3-6Naphthenic base, C3-6Naphthenic base C1-2Alkyl, N-C3-6Cycloalkyl amino carbonyl, N-C3-6Naphthenic base C1-2Alkyl amino Carbonyl, C3-4Cyclo alkoxy carbonyl, C3-4Naphthenic base C1-2Alkoxy carbonyl, phenyl, phenyl C1-2Alkyl, phenoxy group C1-2Alkyl, benzene Base C1-2Alkyl alkylthio base, N- phenyl amino carbonyls, heterocyclyl moieties therein be comprising 1,2 or 3 independently selected from by O, S, N or S (O)24 yuan of the ring members of the group of composition to 6 yuan of non-aromatic rings and condition, which is the heterocycle, cannot contain 2 and be selected from O and S Continuous atom heterocycle, Heterocyclylcarbonyl, heteroaryl moieties therein are independently chosen from N, O and S comprising 1,2 or 3 Heteroaryl, the heteroaryl C of heteroatomic 5 yuan or 6 yuan aromatic rings1-2Alkyl, heteroaryloxy C1-2Alkyl, benzodioxole Base, and any of the wherein described naphthenic base, phenyl, heterocycle, heteroaryl and benzodioxole base part Optionally R is selected from by 1,2 or 312Can be identical or different substituent group substitution；And
R12It is fluorine, chlorine, bromine, methyl, ethyl or methoxyl group.
8. according to the compound described in claim 6 or claim 7, wherein Z4It is pyrazolyl, imidazole radicals or triazolyl, wherein Pyrazolyl, imidazole radicals or triazolyl are optionally selected from R by 1 or 210Can be identical or different substituent group substitution；Or pyrazoles Base, imidazole radicals or triazolyl are optionally selected from R by 111Substituent group substitution and optionally further by 1 be selected from R10's Substituent group replaces.
9. compound according to claim 8, wherein Z4It is pyrazol-1-yl, 1,2,3-triazoles -1- bases or 1,2,4- triazoles - 1- bases, wherein pyrazol-1-yl are optionally selected from R by 110Or R11Substituent group substitution, wherein R10It is hydroxycarbonyl group, methoxyl group Carbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, tert-butoxycarbonyl, amino carbonyl, methylaminocarbonyl, Ethyl aminocarbonyl, methoxyethylamino carbonyl, propargyl-amino carbonyl, N- morpholines and amino carbonyl, N, N- dimethylaminos Base carbonyl, N, N- diethylaminocarbonyls, N- methyl-N-methoxies amino carbonyl or N- Methoxyamino carbonyls, and R11It is Cyclopropylaminocarbonyl, cyclobutylaminocarbonyl, cyclopentylaminocarbonyl or cyclohexylaminocarbonyl；And
1,2,3-triazoles -1- bases or 1,2,4- triazol-1-yls are optionally selected from R by 110Or R11Substituent group substitution, wherein R10 It is cyano, acetenyl, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxyl group, ethoxy carbonyl or ethoxyl methyl, and R11It is Cyclopropyl.
10. compound according to any one of claim 1 to 5, wherein Z are Z6, selected from indyl, indazolyl, benzo Imidazole radicals, pyrrolopyridinyl or triazolo pyridyl.
11. compound according to claim 10, wherein：
Indyl, indazolyl, benzimidazolyl, pyrrolopyridinyl or triazolo pyridyl are optionally selected from R by 1,2 or 314 Can be identical or different substituent group substitution, wherein R14It is cyano, halogen, hydroxyl, formoxyl, C1-4Alkyl, C1-4Alkyl halide Base, C1-4Alkoxy, C1-4Alkyl-carbonyl or C1-4Alkoxy carbonyl；Or
Indyl, indazolyl, benzimidazolyl, pyrrolopyridinyl or triazolo pyridyl are optionally selected from R by 115Take Replace for base and is optionally further selected from R by 1 or 214Substituent group substitution, wherein R15It is pyridyl group, benzo dioxa Cyclopentenyl oxygroup, phenoxy group or Phenylsulfanyl, wherein phenoxy group and Phenylsulfanyl optionally by 1,2 or 3 selected from chlorine, The substituent group substitution that can be identical or different of fluorine, bromine, methyl, ethyl, methoxyl group and ethyoxyl.
12. a kind of agrochemical composition includes the tool according to any one of claim 1 to 11 of effective fungicidal amount There is the compound of formula (I).
13. composition according to claim 12 further includes at least one other active constituent and/or agriculturalization Acceptable diluent or carrier on.
14. it is a kind of for controlling or preventing the method that useful plant is infected by cause enic microorganisms, wherein by antifungal effective The compound according to any one of claim 1 to 11 with formula (I) of amount, or comprising this compound as activity The composition of ingredient is applied to these plants, its part or its place.
15. purposes of the compound according to any one of claim 1 to 11 with formula (I) as fungicide.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110650956A (en) * 2017-04-06 2020-01-03 Fmc公司 Fungicidal oxadiazoles
CN111592494A (en) * 2020-06-05 2020-08-28 中国农业大学 Pyrazole formaldehyde oxime ether compound and preparation method and application thereof
CN111909178A (en) * 2020-08-18 2020-11-10 重庆西米瑞医药技术有限公司 Tazobactam key intermediate and preparation method thereof
WO2021057998A1 (en) * 2019-09-29 2021-04-01 上海森辉医药有限公司 Preparation method for pyrroloaminopyridazinone compound

Families Citing this family (180)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114395005A (en) 2016-01-08 2022-04-26 艾库斯生物科学有限公司 Modulators of extracellular 5' -nucleotidase and uses thereof
UY37062A (en) * 2016-01-08 2017-08-31 Syngenta Participations Ag DERIVATIVES OF ARYL OXADIAZOL FUNGICIDAS
AR108745A1 (en) * 2016-06-21 2018-09-19 Syngenta Participations Ag MICROBIOCIDES OXADIAZOL DERIVATIVES
US11066396B2 (en) 2016-06-23 2021-07-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (HDAC6) inhibitors
UY37623A (en) * 2017-03-03 2018-09-28 Syngenta Participations Ag DERIVATIVES OF OXADIAZOL THIOPHEN FUNGICIDES
EP3630753A1 (en) * 2017-06-02 2020-04-08 Syngenta Participations AG Microbiocidal oxadiazole derivatives
KR20200022452A (en) * 2017-06-28 2020-03-03 신젠타 파티서페이션즈 아게 Fungicidal composition
WO2019002158A1 (en) * 2017-06-30 2019-01-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
AR112221A1 (en) 2017-07-05 2019-10-02 Fmc Corp FUNGICIDE OXADIAZOLES, COMPOSITION THAT INCLUDE THEM AND A METHOD TO CONTROL PHYTO DISEASES THAT USE THEM
WO2019011928A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011923A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011929A1 (en) * 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
BR112020000457A2 (en) * 2017-07-11 2020-07-21 Syngenta Participations Ag microbiocidal oxadiazole derivatives
WO2019012003A1 (en) * 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
AU2018306054A1 (en) * 2017-07-27 2020-01-30 Nippon Soda Co., Ltd. Oxadiazole compound and fungicide for agricultural and horticultural use
WO2019020501A1 (en) 2017-07-28 2019-01-31 Basf Se Preparation of substituted 3-aryl-5-trifluoromethyl-1,2,4-oxadiazoles
EP3713936B1 (en) 2017-11-23 2021-10-20 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019150219A2 (en) * 2018-01-30 2019-08-08 Pi Industries Ltd. Novel oxadiazoles
EP3762367A1 (en) 2018-03-09 2021-01-13 PI Industries Ltd. Heterocyclic compounds as fungicides
WO2019224160A1 (en) 2018-05-25 2019-11-28 Syngenta Participations Ag Microbiocidal picolinamide derivatives
BR112020026877A2 (en) 2018-06-29 2021-04-06 Syngenta Crop Protection Ag MICROBIOCIDAL OXADIAZOL DERIVATIVES
EP3818058A1 (en) 2018-07-02 2021-05-12 Syngenta Crop Protection AG 3-(2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole derivatives as agrochemical fungicides
EP3823966A1 (en) 2018-07-16 2021-05-26 Syngenta Crop Protection AG Microbiocidal oxadiazole derivatives
GB201812692D0 (en) 2018-08-03 2018-09-19 Syngenta Participations Ag Microbiocidal compounds
WO2020032071A1 (en) 2018-08-08 2020-02-13 日本農薬株式会社 Oxadiazoline compound or salt thereof, agricultural or horticultural bactericide containing said compound, and use method therefor
UY38367A (en) 2018-09-13 2020-04-30 Syngenta Participations Ag PESTICIDALLY ACTIVE AZOL-AMIDE COMPOUNDS
UY38366A (en) 2018-09-13 2020-04-30 Syngenta Participations Ag PESTICIDALLY ACTIVE AZOL-AMIDE COMPOUNDS
WO2020070611A1 (en) 2018-10-01 2020-04-09 Pi Industries Ltd Oxadiazoles as fungicides
BR112021005507A2 (en) 2018-10-01 2021-06-15 Pi Industries Ltd. new oxadiazoles
AR116628A1 (en) 2018-10-18 2021-05-26 Syngenta Crop Protection Ag MICROBIOCIDAL COMPOUNDS
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BR112021008675A2 (en) 2018-11-05 2021-08-10 Syngenta Participations Ag pesticide active azole-amide compounds
AR117200A1 (en) 2018-11-30 2021-07-21 Syngenta Participations Ag THIAZOL DERIVATIVES MICROBIOCIDES
AR117183A1 (en) 2018-11-30 2021-07-14 Syngenta Crop Protection Ag THIAZOL DERIVATIVES MICROBIOCIDES
WO2020165403A1 (en) 2019-02-15 2020-08-20 Syngenta Crop Protection Ag Phenyl substituted thiazole derivatives as microbiocidal compounds
EP3696175A1 (en) 2019-02-18 2020-08-19 Syngenta Crop Protection AG Pesticidally active azole-amide compounds
WO2020169526A1 (en) 2019-02-18 2020-08-27 Syngenta Crop Protection Ag Pesticidally-active cyanamide heterocyclic compounds
ES2953140T3 (en) 2019-03-08 2023-11-08 Syngenta Crop Protection Ag Pesticide-active azole-amide compounds
JP2022525967A (en) 2019-03-20 2022-05-20 シンジェンタ クロップ プロテクション アクチェンゲゼルシャフト Pesticide active azoleamide compound
CN113597424A (en) 2019-03-20 2021-11-02 先正达农作物保护股份公司 Pesticidally active azoleamide compounds
GB201903942D0 (en) 2019-03-22 2019-05-08 Syngenta Crop Protection Ag Microbiocidal compounds
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US20220287221A1 (en) 2019-08-21 2022-09-15 Syngenta Participations Ag Precision treatment and sowing or planting method and device
BR112022003177A2 (en) 2019-08-21 2022-05-17 Syngenta Participations Ag Apparatus and method for reducing the development of dust in seeding by precision drilling
BR112022003060A2 (en) 2019-08-21 2022-05-10 Syngenta Participations Ag Apparatus and method for converting existing seeding equipment
WO2021037614A1 (en) 2019-08-23 2021-03-04 Syngenta Crop Protection Ag Pesticidally active pyrazine-amide compounds
GB201912595D0 (en) 2019-09-02 2019-10-16 Syngenta Crop Protection Ag Plant growth regulator compounds
JP2022549417A (en) 2019-09-20 2022-11-25 シンジェンタ クロップ プロテクション アクチェンゲゼルシャフト Pesticidal active heterocyclic derivatives with sulfur- and sulfoximine-containing substituents
UY38885A (en) 2019-09-20 2021-04-30 Syngenta Crop Protection Ag PESTICIDALLY ACTIVE COMPOUNDS OF AZETIDINIL-, PYRROLIDINIL-, PIPERDINIL- OR PIPERAZINYL-PYRIDINYL CARBONYL
WO2021083936A1 (en) 2019-11-01 2021-05-06 Syngenta Crop Protection Ag Pesticidally active fused bicyclic heteroaromatic compounds
CN114616231A (en) 2019-11-07 2022-06-10 日本农药株式会社 Oxadiazoline compound or salt thereof, agricultural or horticultural fungicide containing the same, and method for using the same
CN115003666A (en) 2019-12-04 2022-09-02 先正达农作物保护股份公司 Pesticidally active fused bicyclic heteroaromatic amino compounds
WO2021122645A1 (en) 2019-12-20 2021-06-24 Syngenta Crop Protection Ag Pesticidally active azole-amide compounds
JP2023510175A (en) 2019-12-31 2023-03-13 シンジェンタ クロップ プロテクション アクチェンゲゼルシャフト Pesticidal active heterocyclic derivatives with sulfur-containing substituents
AR120982A1 (en) 2020-01-06 2022-04-06 Syngenta Crop Protection Ag HETEROCYCLIC DERIVATIVES ACTIVE AS PESTICIDES WITH SUBSTITUENTS CONTAINING SULFUR
WO2021144354A1 (en) 2020-01-15 2021-07-22 Syngenta Crop Protection Ag Pesticidally-active bicyclic heteroaromatic compounds
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JP2023513047A (en) 2020-01-30 2023-03-30 シンジェンタ クロップ プロテクション アクチェンゲゼルシャフト Pesticidal effective condensed bicyclic aromatic heterocyclic amino compounds
EP4103549A1 (en) 2020-02-11 2022-12-21 Syngenta Crop Protection AG Pesticidally active cyclic amine compounds
US20230143596A1 (en) 2020-02-27 2023-05-11 Syngenta Crop Protection Ag Pesticidally active diazine-bisamide compounds
WO2021175822A1 (en) 2020-03-02 2021-09-10 Syngenta Crop Protection Ag Pesticidally amidine-substituted benzoic acid amide compounds
EP4114185A1 (en) * 2020-03-04 2023-01-11 Basf Se Use of substituted 1,2,4-oxadiazoles for combating phytopathogenic fungi
UY39115A (en) 2020-03-05 2021-10-29 Syngenta Crop Protection Ag FUNGICIDE MIXTURES OF ARYL METHOXYACRYLATE DERIVATIVES
AU2021232616A1 (en) 2020-03-05 2022-09-22 Syngenta Crop Protection Ag Fungicidal compositions
US11633416B1 (en) 2020-03-06 2023-04-25 Arcus Biosciences, Inc. Oral formulations of CD73 compounds
CN115297727A (en) 2020-03-13 2022-11-04 先正达农作物保护股份公司 Method for controlling or preventing plant infection by phytopathogen microorganism corynebacterium polyspora
BR112022018269A2 (en) 2020-03-13 2022-12-27 Syngenta Crop Protection Ag METHODS FOR CONTROL OR PREVENTION OF PLANT INFESTATION BY THE PHYTOPATHOGENIC MICROORGANISM CORYNESPORA CASSIICOLA
CN115315186A (en) 2020-03-13 2022-11-08 先正达农作物保护股份公司 Method for controlling or preventing plant infection by phytopathogen microorganism corynebacterium polyspora
BR112022018295A2 (en) 2020-03-13 2022-10-25 Syngenta Crop Protection Ag METHODS OF CONTROL OR PREVENTION OF PLANT INFESTATION BY THE PHYTOPATOGENIC MICRO-ORGANISM CORYNESPORA CASSIICOLA, CERCOSPORA SOJINA AND/OR CERCOSPORA KIKUCHII
WO2021180596A1 (en) 2020-03-13 2021-09-16 Syngenta Crop Protection Ag Methods of controlling or preventing infestation of plants by the phytopathogenic microorganism corynespora cassiicola
BR112022018280A2 (en) 2020-03-13 2022-10-25 Syngenta Crop Protection Ag METHODS OF CONTROL OR PREVENTION OF PLANT INFESTATION BY THE PHYTOPATOGENIC MICRO-ORGANISM CORYNESPORA CASSIICOLA
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CN112979627B (en) * 2021-03-08 2023-08-22 浙江工业大学 Pyrazole bi-1, 2, 4-oxadiazole substituted benzamide compound and preparation method and application thereof
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CA3221102A1 (en) 2021-06-02 2022-12-08 Michel Muehlebach Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
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WO2023275116A1 (en) 2021-07-02 2023-01-05 Syngenta Crop Protection Ag Use of fluazifop-p-butyl for insect control
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WO2024068947A1 (en) 2022-09-30 2024-04-04 Syngenta Crop Protection Ag Microbiocidal pyrazole derivatives

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132507A (en) * 1993-08-11 1996-10-02 拜尔公司 Substituted Azadioxacycloalkens and their use as fungicides
CN102361867A (en) * 2009-01-23 2012-02-22 百时美施贵宝公司 Substituted oxadiazole derivatives as s1p agonists in the treatment of autoimmune and inflammatory diseases
CN103102348A (en) * 2011-11-14 2013-05-15 上海交通大学 Oxadiazole compound and preparation method thereof, medicine composition and application thereof
WO2015185485A1 (en) * 2014-06-06 2015-12-10 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi

Family Cites Families (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0276432A3 (en) 1986-12-12 1988-10-26 Ciba-Geigy Ag Pesticides
CN100556905C (en) 2005-09-08 2009-11-04 国家南方农药创制中心江苏基地 Pyrazol acid amide compounds and intermediate thereof and be the pest control agent of activeconstituents with this compounds
CL2007002787A1 (en) 2006-09-29 2008-05-30 Bayer Cropscience Sa COMPOUNDS DERIVED FROM N-CICLOALQUIL-CARBOXAMIDA, N-CICLOALQUIL-TIOCARBOXAMIDA AND N-CICLOALQUIL-CARBOXAMIDAMIDA N-SUBSTITUTED; FUNGICIDE COMPOSITION THAT INCLUDES SUCH COMPOUNDS; AND METHOD TO COMBAT FITOPATOGEN CULTURE FUNGIANS THAT YOU UNDERSTAND
WO2011088181A1 (en) 2010-01-13 2011-07-21 Tempero Pharmaceuticals, Inc. Compounds and methods
US8981084B2 (en) 2010-01-13 2015-03-17 Tempero Pharmaceuticals, Inc. Oxadiazole HDAC inhibitors
BR112012020521B1 (en) 2010-02-17 2017-12-26 Syngenta Participations Ag DERIVATIVE COMPOUNDS OF ISOXAZOLINE, ITS INTERMEDIARIES AND METHOD FOR CONTROLING INSECTS, MITES, NEMATODES, OR MOLLUSCS
UA107865C2 (en) 2010-10-21 2015-02-25 Байєр Інтелекчуал Проперті Гмбх Heterocyclic carboxamides
WO2013006408A1 (en) 2011-07-01 2013-01-10 Tempero Pharmaceuticals, Inc. Compounds and methods
EP2729454B1 (en) * 2011-07-08 2015-09-16 Novartis AG Novel trifluoromethyl-oxadiazole derivatives and their use in the treatment of disease
WO2013009830A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013009810A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013009827A1 (en) 2011-07-13 2013-01-17 Tempero Pharmaceuticals, Inc. Methods of treatment
WO2013066835A2 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
WO2013066839A2 (en) 2011-10-31 2013-05-10 Glaxosmithkline Llc Compounds and methods
CN103081916B (en) * 2011-11-02 2014-08-06 中国中化股份有限公司 Application of pyrazole amide compound as agricultural bactericide
EA201491060A1 (en) 2011-11-28 2014-09-30 Новартис Аг NEW DERIVATIVES OF TRIFTOROMETHYLOROXIAZOLE AND THEIR APPLICATION FOR THE TREATMENT OF DISEASE
WO2015055706A2 (en) 2013-10-16 2015-04-23 Bayer Cropscience Ag N-cycloalkyl-n-(biheterocyclymethylene)-(thio)carboxamide derivatives
US10081624B2 (en) 2014-08-26 2018-09-25 Takeda Pharmaceutical Company Limited Heterocyclic compound
WO2017033946A1 (en) 2015-08-25 2017-03-02 武田薬品工業株式会社 Heterocyclic compound
WO2017076757A1 (en) 2015-11-02 2017-05-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017076739A1 (en) 2015-11-03 2017-05-11 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi
EP3165094A1 (en) 2015-11-03 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017076935A1 (en) 2015-11-04 2017-05-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018008288A2 (en) 2015-11-04 2018-10-30 Basf Se use of formula compounds, formula compounds, mixture, agrochemical composition and method for combating fungi
EP3165093A1 (en) 2015-11-05 2017-05-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
MX2018005388A (en) 2015-11-05 2018-08-16 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi.
AR106679A1 (en) 2015-11-13 2018-02-07 Basf Se OXADIAZOLS REPLACED TO FIGHT FITOPATHOGEN FUNGI
WO2017081309A1 (en) 2015-11-13 2017-05-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US20180354920A1 (en) 2015-11-13 2018-12-13 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017081312A1 (en) 2015-11-13 2017-05-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US10499644B2 (en) 2015-11-19 2019-12-10 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3376868A1 (en) * 2015-11-19 2018-09-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
JP6930972B2 (en) * 2015-12-02 2021-09-01 シンジェンタ パーティシペーションズ アーゲー Microbial oxadiazole derivative
CN108366564A (en) 2015-12-03 2018-08-03 巴斯夫欧洲公司 Qu Dai oxadiazole classes for preventing plant pathogenic fungi
JP6841234B2 (en) 2015-12-25 2021-03-10 住友化学株式会社 Oxadiazole compounds and their uses
WO2017110864A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Plant disease control composition and application for same
WO2017110862A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compound and use thereof
WO2017110861A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Plant disease control agent containing oxadiazole compound
WO2017111152A1 (en) 2015-12-25 2017-06-29 住友化学株式会社 Oxadiazole compounds and use thereof
UY37062A (en) * 2016-01-08 2017-08-31 Syngenta Participations Ag DERIVATIVES OF ARYL OXADIAZOL FUNGICIDAS
CN109071520B (en) 2016-03-24 2022-06-14 先正达参股股份有限公司 Microbicidal oxadiazole derivatives
WO2017169893A1 (en) 2016-03-31 2017-10-05 住友化学株式会社 Oxadiazole compound and use thereof
CA3020532A1 (en) 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
JP2017190296A (en) 2016-04-13 2017-10-19 住友化学株式会社 Pest control composition and use therefor
WO2017211652A1 (en) 2016-06-09 2017-12-14 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018074559A2 (en) 2016-06-09 2019-03-12 Basf Se compounds, agrochemical composition, use of compounds and method to combat phytopathogenic harmful fungi
EP3468958B1 (en) 2016-06-09 2020-12-16 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2017213252A1 (en) 2016-06-10 2017-12-14 Sumitomo Chemical Company, Limited Oxadiazole compound and use as pesticide
US11066396B2 (en) 2016-06-23 2021-07-20 Merck Sharp & Dohme Corp. 3-aryl- heteroaryl substituted 5-trifluoromethyl oxadiazoles as histonedeacetylase 6 (HDAC6) inhibitors
AR109304A1 (en) 2016-08-10 2018-11-21 Sumitomo Chemical Co OXADIAZOL COMPOUND AND ITS USE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132507A (en) * 1993-08-11 1996-10-02 拜尔公司 Substituted Azadioxacycloalkens and their use as fungicides
CN102361867A (en) * 2009-01-23 2012-02-22 百时美施贵宝公司 Substituted oxadiazole derivatives as s1p agonists in the treatment of autoimmune and inflammatory diseases
CN103102348A (en) * 2011-11-14 2013-05-15 上海交通大学 Oxadiazole compound and preparation method thereof, medicine composition and application thereof
WO2015185485A1 (en) * 2014-06-06 2015-12-10 Basf Se Use of substituted oxadiazoles for combating phytopathogenic fungi

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110650956A (en) * 2017-04-06 2020-01-03 Fmc公司 Fungicidal oxadiazoles
CN110650956B (en) * 2017-04-06 2024-03-08 Fmc公司 Fungicidal oxadiazoles
WO2021057998A1 (en) * 2019-09-29 2021-04-01 上海森辉医药有限公司 Preparation method for pyrroloaminopyridazinone compound
CN111592494A (en) * 2020-06-05 2020-08-28 中国农业大学 Pyrazole formaldehyde oxime ether compound and preparation method and application thereof
CN111909178A (en) * 2020-08-18 2020-11-10 重庆西米瑞医药技术有限公司 Tazobactam key intermediate and preparation method thereof

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